WO2018131569A1 - Epoxy resin composition - Google Patents

Epoxy resin composition Download PDF

Info

Publication number
WO2018131569A1
WO2018131569A1 PCT/JP2018/000200 JP2018000200W WO2018131569A1 WO 2018131569 A1 WO2018131569 A1 WO 2018131569A1 JP 2018000200 W JP2018000200 W JP 2018000200W WO 2018131569 A1 WO2018131569 A1 WO 2018131569A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
carbon atoms
ring
atom
Prior art date
Application number
PCT/JP2018/000200
Other languages
French (fr)
Japanese (ja)
Inventor
矩章 福田
良太 針▲崎▼
山本　勝政
Original Assignee
住友精化株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 住友精化株式会社 filed Critical 住友精化株式会社
Priority to KR1020197021281A priority Critical patent/KR102461516B1/en
Priority to EP18738684.2A priority patent/EP3569628B1/en
Priority to JP2018561366A priority patent/JP6553310B2/en
Priority to US16/476,679 priority patent/US20200385514A1/en
Priority to CN201880006382.5A priority patent/CN110167989B/en
Publication of WO2018131569A1 publication Critical patent/WO2018131569A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/302—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/308—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
    • C08G59/3263—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
    • C08G59/3281—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
    • C08G59/329—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
    • C08G59/4269—Macromolecular compounds obtained by reactions other than those involving unsaturated carbon-to-carbon bindings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0333—Organic insulating material consisting of one material containing S
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2190/00—Compositions for sealing or packing joints

Definitions

  • the present invention relates to an epoxy resin composition, a method for producing the same, a use of the composition, and the like.
  • Patent Document 1 describes that an epoxy resin composition containing a specific epoxy resin and a specific active ester compound has high adhesion and low dielectric loss tangent characteristics.
  • an epoxy resin composition containing a specific epoxy resin containing a silicon atom and an active ester compound has excellent low dielectric properties. I found it. Based on this knowledge, further studies have been made and the present invention has been completed.
  • ring X is a saturated hydrocarbon ring or unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed or connected
  • R Xa , R Xb , R Xc , and R Xd are the same or different and are a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyl group, a halogen atom, or formula (3):
  • R 1 is the same or different and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group.
  • the carbon atom may be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom;
  • R 2 represents an alkylene group having 1 to 18 carbon atoms, and this group is at least one selected from the group consisting of oxygen atoms and nitrogen atoms, with some carbon atoms excluding carbon atoms directly bonded to silicon atoms.
  • R 3 s are the same or different and each represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and these groups have a part of carbon atoms, May be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom, m represents an integer of 0 to 6, n represents an integer of 0 to 3.
  • R Xa , R Xb , R Xc , and R Xd is a group represented by the formula (3),
  • a hydrogen atom bonded to a carbon atom constituting a hydrocarbon ring constituting the X ring and to which R Xa , R Xb , R Xc , and R Xd are not bonded is a lower alkyl group or a lower alkoxy group , A lower alkenyl group, or a halogen atom.
  • ring X 1 and ring X 2 are the same or different and each represents a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, and Y is a bond, substituted with an alkyl group having 1 to 4 carbon atoms. Or a ring represented by an alkylene group having 1 to 6 carbon atoms, an oxygen atom (—O—), a sulfur atom (—S—), —SO—, or —SO 2 —).
  • the saturated hydrocarbon ring is a saturated hydrocarbon ring having 4 to 8 carbon atoms;
  • the unsaturated hydrocarbon ring is an unsaturated hydrocarbon ring having 4 to 8 carbon atoms; Item 3.
  • X ii represents a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed, to two hydrogen atoms
  • Y represents a bond, an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, an oxygen atom (—O—), a sulfur atom (—S—), -SO- or -SO 2- )).
  • R 1 s are the same or different and each represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and these groups have a part of carbon atoms, May be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom
  • R 2 is the same or different and represents an alkylene group having 1 to 18 carbon atoms, and this group is selected from the group consisting of oxygen atoms and nitrogen atoms, with some carbon atoms excluding carbon atoms directly bonded to silicon atoms.
  • R 3 s are the same or different and each represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and these groups have a part of carbon atoms, May be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom, m represents an integer of 0 to 6, n represents an integer of 0 to 3. ) And an epoxy resin represented by the formula (1-iiia):
  • X iii is a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed, to 3 hydrogen atoms
  • Item 2 The epoxy resin composition according to Item 1, comprising at least one epoxy resin selected from the group consisting of epoxy resins represented by the formula (1) and an active ester compound.
  • Item 5. The epoxy resin composition according to any one of Items 1 to 4, wherein the active ester compound is a compound having two or more ester groups in one molecule.
  • Item 6. Item 1.
  • the active ester compound is a condensate of at least one selected from the group consisting of carboxylic acid compounds and thiocarboxylic acid compounds and at least one selected from the group consisting of hydroxy compounds and thiol compounds. 4.
  • Item 7. Item 5. The epoxy resin composition according to any one of Items 1 to 4, wherein the active ester compound is an ester compound containing a dicyclopentadienyl diphenol structure.
  • Item 8. Item 8. A cured product of the epoxy resin composition according to any one of Items 1 to 7.
  • Item 9. A semiconductor encapsulant, a liquid encapsulant, a potting material, a sealing material, an interlayer insulating film, an adhesive layer, wherein the epoxy resin composition according to any one of Items 1 to 7 or the cured product according to Item 8 is used, Coverlay film, electromagnetic shielding film, printed circuit board material or composite material.
  • any one of Items 1 to 7 used for a semiconductor encapsulant, a liquid encapsulant, a potting material, a sealant, an interlayer insulating film, an adhesive layer, a cover lay film, an electromagnetic shielding film, a printed circuit board material, or a composite material Item 9.
  • Item 1 to 7 for producing a semiconductor encapsulant, liquid encapsulant, potting material, sealing material, interlayer insulating film, adhesive layer, coverlay film, electromagnetic wave shielding film, printed circuit board material or composite material Use of the epoxy resin composition according to Item 8 or the cured product according to Item 8.
  • the cured product has excellent electrical characteristics and high adhesive strength to metal. Therefore, the epoxy resin composition of the present invention includes, for example, a semiconductor sealing body, a liquid sealing material, a potting material, a sealing material, an interlayer insulating film, an adhesive layer, a cover lay film, an electromagnetic wave shielding film, a printed board material, and a composite material. It can be suitably used for a wide range of uses.
  • the epoxy resin composition included in the present invention has the formula (1):
  • R Xa , R Xb , R Xc , and R Xd are the same or different and are a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyl group, a halogen atom, or the formula (3):
  • lower alkyl group, the lower alkoxy group, and the lower alkenyl group may be collectively referred to as “lower carbon substituent”.
  • lower carbon substituents among the lower carbon substituents, a lower alkyl group or a lower alkoxy group is more preferable.
  • R Xa , R Xb , R Xc , and R Xd are a group of the formula (3).
  • R Xa , R Xb , R Xc , and R Xd are three hydrogen atoms or halogen atoms or lower carbon substituents and one is a group of formula (3), or two are hydrogen atoms or halogen atoms or Two of the lower carbon substituents are groups of formula (3), one is a hydrogen atom or halogen atom or lower carbon substituent and three are groups of formula (3), or all are of formula (3) It is a group.
  • R Xa , R Xb , R Xc , and R Xd are a hydrogen atom, a halogen atom, or a lower carbon substituent
  • R Xd is a formula (Ii) R Xa and R Xb are a hydrogen atom, a halogen atom or a lower carbon substituent, and R Xc and R Xd are a group of formula (3), or (iii) R Xa Is a hydrogen atom or a halogen atom or a lower carbon substituent, and R Xb , R Xc , and R Xd are groups of the formula (3), or (iv) all of R Xa , R Xb , R Xc , and R Xd Can be a group of formula (3).
  • R Xa , R Xb , R Xc , and R Xd are a group of formula (3).
  • R Xa , R Xb , R Xc , and R Xd may be the same or different. Therefore, (i) when R Xa , R Xb and R Xc are a hydrogen atom, a halogen atom or a lower carbon substituent and R Xd is a group of formula (3), R Xa , R Xb and R Xc are the same or (Ii) when R Xa and R Xb are a hydrogen atom, a halogen atom or a lower carbon substituent and R Xc and R Xd are a group of formula (3), R Xa and R Xb are the same or different R Xc and R Xd may be the same or different, and (iii) R Xa is a hydrogen atom, a halogen atom, or a lower carbon substituent, and R Xb , R Xc , and R Xd are a group of the formula (3) If, R Xa ,
  • R Xa , R Xb , R Xc , and R Xd are halogen atoms or lower carbon substituents
  • these halogen atoms or lower carbon substituents may be the same or different.
  • it is more preferable that 2 or 3 of R Xa , R Xb , R Xc , and R Xd are the same lower carbon substituent.
  • the lower carbon substituent refers to a lower alkyl group, a lower alkoxy group, or a lower alkenyl group.
  • “lower” means 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6).
  • a lower alkyl group or a lower alkoxy group is preferred.
  • Specific examples of the lower alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.
  • Preferred examples of the lower alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group.
  • the halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a fluorine atom, a chlorine atom, or a bromine atom, and more preferably a fluorine atom or a bromine atom.
  • the X ring represents a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed or connected.
  • the saturated hydrocarbon ring for example, a saturated hydrocarbon ring having 4 to 8 carbon atoms (4, 5, 6, 7, or 8) is preferable, and a cyclopentane ring, a cyclohexane ring and the like are particularly preferable.
  • the unsaturated hydrocarbon ring for example, an unsaturated hydrocarbon ring having 4 to 8 carbon atoms (4, 5, 6, 7, or 8) is preferable, and a benzene ring or the like is particularly preferable.
  • the saturated hydrocarbon ring and / or unsaturated hydrocarbon rings is 2, 3, Alternatively, a ring having 4 condensed rings is preferable, and a ring having 2 or 3 condensed rings is more preferable.
  • decahydronaphthalene ring More specifically, for example, decahydronaphthalene ring, adamantane ring, naphthalene ring, phenanthrene ring, anthracene ring, pyrene ring, triphenylene ring, tetralin ring, 1,2,3,4,5,6,7,8- Examples include an octahydronaphthalene ring and a norbornene ring.
  • a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed is collectively referred to as a “hydrocarbon ring”. May be called.
  • the ring represented by is preferable.
  • the X 1 ring and the X 2 ring are the same or different and represent a saturated hydrocarbon ring or an unsaturated hydrocarbon ring. That is, the X 1 ring and the X 2 ring are both saturated hydrocarbon rings, or both are unsaturated hydrocarbon rings, or one is a saturated hydrocarbon ring and the other is an unsaturated hydrocarbon ring. It is preferable that both the X 1 ring and the X 2 ring are saturated hydrocarbon rings or both are unsaturated hydrocarbon rings.
  • the X 1 ring and the X 2 ring are preferably both benzene rings, both cyclohexane rings, or one is a benzene ring and the other is a cyclohexane ring, and more preferably both are benzene rings.
  • Y represents a bond, an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, an oxygen atom (—O—), a sulfur atom (—S—), —SO. -Or -SO 2 -is shown.
  • the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group.
  • alkyl group having 1 to 4 carbon atoms as a substituent examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.
  • Preferred examples of the alkylene group having 1 to 6 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms include —CH (CH 3 ) —, —C (CH 3 ) 2 —, —CH 2 CH (CH 3 ) CH. Examples thereof include 2- , -CH 2 C (CH 3 ) 2 CH 2- and the like.
  • Y is preferably a bond, an oxygen atom, a methylene group, a dimethylmethylene group, —S—, —SO 2 —, and more preferably a bond, a dimethylmethylene group, an oxygen atom, —SO 2 —.
  • the ring represented by formula (2) is substituted with R Xa , R Xb , R Xc , and R Xd .
  • the ring X in the formula (1) is a ring represented by the formula (2), and three of R Xa to R Xd are a hydrogen atom, a halogen atom or a lower carbon substituent, and one is a group of the formula (3) In this case, either ring X 1 or ring X 2 may be substituted with a group of formula (3).
  • substituted (X 1 ring halogen atom or a lower carbon substituent Number: X 2 ring substitution number) is (1: 0), (0: 1), (2: 0), (1: 1), (0: 2), (3: 0), (2: 1) ), (1: 2), or (0: 3).
  • R Xa to R Xd are a hydrogen atom, a halogen atom or a lower carbon substituent and two are groups of the formula (3)
  • either the X 1 ring or the X 2 ring is a group of the formula (3) in may be substituted, X 1 ring and X 2 rings may be substituted by one by one group of the formula (3), X 1 ring and X 2 ring group of the formula (3) one by one It is preferably substituted with.
  • a halogen atom or a lower carbon substituent when the ring represented by formula (2) is substituted with 0, 1, or 2 halogen atom or a lower carbon substituent group, a halogen atom or a lower carbon substituent (X 1 substitution number rings: X 2 ring substitution number) can be (1: 0), (0: 1), (2: 0), (1: 1), or (0: 2).
  • R Xa to R Xd is a hydrogen atom, a halogen atom or a lower carbon substituent, and three are groups of the formula (3)
  • either the X 1 ring or the X 2 ring is a group of the formula (3) May be substituted with two X 1 rings
  • one X 2 ring may be substituted with one group of formula (3), one X 1 ring and two X 2 rings with formula (3)
  • two X 1 rings are substituted with one X 2 group or one X 1 ring and two X 2 rings are represented by formula (3).
  • the ring represented by the formula (2) is substituted with 0 or 1 halogen atom or lower carbon substituent, and the halogen atom or lower carbon substituent (the number of substitution of X 1 ring: X 2 ring) The number of substitutions) may be (1: 0) or (0: 1).
  • R Xa to R Xd are groups of the formula (3)
  • either the X 1 ring or the X 2 ring may be substituted with four groups of the formula (3), and the X 1 ring is 3
  • One X 2 ring may be substituted with one group of formula (3)
  • one X 1 ring may be substituted with three X 2 rings with three groups of formula (3)
  • X 1 ring There may be substituted with two X 2 rings two formulas (3) group, it is preferred that X 1 ring are two X 2 ring is substituted by two groups of formula (3).
  • ring X is the same as above.
  • a group represented by the following formula is particularly preferable. That is,
  • R 1 is the same or different and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.
  • Part of the carbon atoms may be substituted with at least one atom (preferably an oxygen atom) selected from the group consisting of an oxygen atom and a nitrogen atom.
  • the partial carbon atoms are preferably carbon atoms that are not directly bonded to a silicon atom.
  • the part of carbon atoms that may be substituted is 1 or plural (for example, 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom.
  • R 1 bonded to the same silicon atom in view like the simplicity of the synthesis is preferably the same.
  • it is more preferable that all R 1 existing in the formula (1) is the same.
  • the alkyl group having 1 to 18 carbon atoms represented by R 1 is a linear or branched alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl.
  • n-butyl group n-pentyl group, neopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, 2,2,4-trimethylpentyl group, n-octyl group, isooctyl group, n- Nonyl group, n-decyl group, n-dodecyl group and the like can be mentioned.
  • An alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is further preferable, and a methyl group is particularly preferable.
  • the alkenyl group having 2 to 9 carbon atoms represented by R 1 is a linear or branched alkenyl group such as vinyl group, allyl group, 2-propenyl group, butenyl group, pentenyl group, hexenyl group, A heptenyl group, an octenyl group, a nonenyl group, etc. are mentioned.
  • An alkenyl group having 2 to 4 carbon atoms is preferred.
  • Examples of the cycloalkyl group represented by R 1 include a 3- to 8-membered cycloalkyl group, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a methylcyclohexyl group.
  • Examples of the aryl group represented by R 1 include a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a naphthyl group. Of these, a phenyl group is preferred.
  • Examples of the aralkyl group represented by R 1 include an alkyl group having 1 to 4 carbon atoms substituted with an aryl group (especially a phenyl group).
  • an aryl group especially a phenyl group.
  • benzyl group, ⁇ -phenethyl group, ⁇ -phenethyl group, ⁇ - Examples thereof include a methylphenethyl group.
  • R 1 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
  • R 2 represents an alkylene group having 1 to 18 carbon atoms.
  • the alkylene group is a linear or branched alkylene group, preferably a linear alkylene group.
  • Examples include a methylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, and a tridecamethylene group.
  • an alkylene group having 2 to 18 carbon atoms preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, and further preferably an alkylene group having 2 to 6 carbon atoms. And particularly preferably an alkylene group having 2 to 5 carbon atoms.
  • some carbon atoms may be substituted with at least one atom (preferably an oxygen atom) selected from the group consisting of an oxygen atom and a nitrogen atom.
  • the partial carbon atom is preferably a carbon atom that is not directly bonded to any of a silicon atom and a 3- to 8-membered ring or an epoxy ring.
  • the part of carbon atoms that may be substituted is 1 or plural (for example, 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom.
  • Examples of the group include, when the side bonded to the silicon atom of R 2 is (*), for example, (*)-alkylene having 2 to 9 carbon atoms-O-alkylene having 1 to 8 carbon atoms, preferably (*)-C2-C4 alkylene-O-C1-C3 alkylene-, more preferably (*)-C2-C4 alkylene-O-C1-C2 alkylene-, especially Preferably, (*)-C3 alkylene-O-methylene- is used.
  • m represents an integer of 0 to 6 (that is, 0, 1, 2, 3, 4, 5, or 6).
  • N represents an integer of 0 to 3 (that is, 0, 1, 2, or 3).
  • group of formula (4) a group to which R 2 of formula (3) is bonded (side not bonded to a silicon atom) is represented by formula (4) (hereinafter, sometimes referred to as “group of formula (4)”). It becomes as follows.
  • n is an integer of 0 to 3, and thus represents any of the following groups.
  • R 2 and R 3 are bonded to a 3- to 8-membered ring or an epoxy ring.
  • n represents the number of R 3 bonded to a 3- to 8-membered ring or an epoxy ring.
  • R 3 is the same or different and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.
  • Part of the carbon atoms may be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom.
  • the partial carbon atom is preferably a carbon atom that is not directly bonded to a 3- to 8-membered ring or an epoxy ring.
  • the part of carbon atoms that may be substituted is 1 or plural (for example, 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom.
  • R 3 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.
  • R 1 , R 2 , R 3 , m, and n are the same as described above, and all of R 1 are the same, and R 3 is present (a plurality is present).
  • groups that are all identical are mentioned.
  • the group is present in the epoxy resin represented by the formula (1) in 1, 2, 3 or 4, and each group may be the same or different, and is preferably the same.
  • R 3 is the same as above, and m is 0, 1, 2, 3 or 4, and n is 0, 1 or 2.
  • R 3 is the same as described above, and m is 0, 1, 2, 3 or 4, and n is 0, 1 or 2.
  • the following groups can be mentioned.
  • the group of the formula (4) is 1, 2, 3 or 4 in the epoxy resin represented by the formula (1), but each group may be the same or different and is preferably the same.
  • a hydrogen atom bonded to a carbon atom constituting a hydrocarbon ring constituting the X ring and to which R Xa , R Xb , R Xc , and R Xd are not bonded is a lower carbon substituent or It may be substituted with a halogen atom (preferably a lower carbon substituent). That is, when the X ring is a saturated hydrocarbon ring or unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed, these rings are constituted.
  • a hydrogen atom bonded to a carbon atom to which R Xa , R Xb , R Xc , and R Xd are not bonded is substituted with a lower carbon substituent or a halogen atom (preferably a lower carbon substituent)
  • a halogen atom preferably a lower carbon substituent
  • the X ring is a ring having a structure in which two saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are connected, these connected saturated hydrocarbon rings and / or unsaturated hydrocarbon rings and R Xa a carbon atom constituting the hydrocarbon ring, R Xb, R Xc, and hydrogen atoms bonded to the carbon atom to which R Xd is not bound is a lower carbon substituent or a halogen atom (preferably lower carbon location It may be substituted by a group).
  • the case where the X ring is a ring represented by the formula (2) will be described more specifically.
  • the carbon atoms constituting the X 1 ring and the X 2 ring, and R Xa , R Xb , R Xc , And a hydrogen atom bonded to a carbon atom to which R Xd is not bonded may be substituted with a lower carbon substituent or a halogen atom (preferably a lower carbon substituent).
  • R Xa-d non-bonded a carbon atom that constitutes a hydrocarbon ring constituting the X ring and to which R Xa , R Xb , R Xc , and R Xd are not bonded.
  • R Xa-d non-bonded Sometimes called a "carbon atom.”
  • R Xa-d non-bonded hydrogen atoms bonded to carbon atoms may be substituted lower carbon substituent group or a halogen atom, it is preferable to only one single R Xa-d unbound carbon atoms bonds. That, R if Xa-d hydrogen atoms bonded to non-bonded carbon atoms is substituted, one hydrogen atom have a lower carbon substituent or a halogen atom of the hydrogen atoms bonded to R Xa-d unbound carbon atoms Is preferably substituted with. Further, the number of substitutions (that is, the total of the lower carbon substituent and the halogen atom) is preferably smaller than the number of R Xa-d non-bonded carbon atoms.
  • the number of the substitution is preferably 1 to 6 (1, 2, 3, 4, 5, or 6), more preferably 1 to 4, and still more preferably 1 to 2.
  • the hydrogen atom to be substituted is preferably a hydrogen atom bonded to a carbon atom to which Y is not bonded.
  • R Xa , R Xb , R Xc , and R Xd is a lower carbon substituent and at least one lower carbon substituent is bonded to an R Xa-d unbonded carbon atom
  • the carbon substituents are the same. That is, if there is a lower carbon substituent in R Xa , R Xb , R Xc , and R Xd and there is a lower carbon substituent bonded to an R Xa-d unbonded carbon atom, all lower carbon substitutions It is preferred that the groups are the same.
  • R Xa , R Xb , R Xc , and R Xd is a halogen atom and at least one halogen atom is bonded to an R Xa-d non-bonded carbon atom, all the halogen atoms are It is preferable that they are the same. That is, when a halogen atom is present in R Xa , R Xb , R Xc , and R Xd and a halogen atom bonded to an R Xa-d unbonded carbon atom is present, all halogen atoms are the same. Is preferred.
  • R Xa , R Xb , R Xc , and R Xd are the same as defined above, and R Xg1 and R Xg2 are the same or different and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group.
  • An epoxy resin represented by a group or a lower alkenyl group is preferred.
  • R Xa , R Xb , R Xc , R Xd , R Xg1 and R Xg2 are bonded to different carbon atoms on the benzene ring, respectively.
  • the epoxy resins represented by the formula (1-X1) those in which R Xg1 and R Xg2 are hydrogen atoms are preferable.
  • R Xa , R Xb , R Xc , and R Xd are the same as above, and R Xg1 and R Xg2 are the same as above). it can.
  • R Xa and R Xb are hydrogen atoms
  • R Xc and R Xd are groups of the formula (3)
  • R Xg1 and R Xg2 are hydrogen atoms.
  • R Xa and R Xc are hydrogen atoms
  • R Xb and R Xd are groups of the formula (3)
  • R Xg1 and R Xg2 are more preferably hydrogen atoms.
  • R Xa is a hydrogen atom
  • R Xb , R Xc and R Xd are groups of the formula (3)
  • R Xg1 and R Xg2 are hydrogen. More preferably, it is an atom.
  • Y is the same as defined above;
  • R Xa , R Xb , R Xc , and R Xd are the same as defined above;
  • R X11 , R X12 , R X13 , and R X21 , R X22 and R X23 may be the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group.
  • R Xa , R Xc , R X11 , R X12 , and R X13 are more preferably bonded to different carbon atoms
  • R Xb , R Xd , R X21 , More preferably, R X22 and R X23 are bonded to different carbon atoms.
  • R Xa , R Xb , R Xc , R Xd , R X11 , R X12 , R X13 , R X21 , R X22 , and R X23 are not bonded to the carbon atom to which Y is bonded.
  • Y is the same as defined above;
  • R Xa , R Xb , R Xc , and R Xd are the same as defined above;
  • R X11 , R X12 , and R X13 and R X21 , R X22 and R X23 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group), or an epoxy resin represented by the formula (1-X2b):
  • Y is the same as defined above;
  • R Xa , R Xb , R Xc , and R Xd are the same as defined above;
  • R X11 , R X12 , R X13 , and R X21 , R X22 and R X23 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group), or an epoxy resin represented by the formula (1-X2c):
  • Y is the same as defined above;
  • R Xa , R Xb , R Xc , and R Xd are the same as defined above;
  • R X11 , R X12 , and R X13 and R X21 , R X22 and R X23 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group.
  • R Xa , R Xb , R Xc , and R Xd are groups of the formula (3), and R X11 and R X21 are lower carbon substituents. Yes , it is preferable that R X12 , R X13 , R X22 , and R X23 are hydrogen atoms.
  • Y is an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms (particularly —C (CH 3 ) 2 —), and R Xa , R Xb , R Xc , And R Xd is a group of the formula (3), R X11 and R X21 are lower alkoxy groups, and R X12 , R X13 , R X22 , and R X23 are particularly preferably hydrogen atoms.
  • R Xa , R Xb , R Xc and R Xd are all the same, and the lower carbon substituents of R X11 and R X21 are the same.
  • R Xa and R Xb are hydrogen atoms
  • R Xc and R Xd are groups of the formula (3)
  • R X11 , R X12 , R X13 , R X21 , R X22 , and R X23 are preferably a hydrogen atom.
  • R Xc and R Xd are the same.
  • R Xa is a hydrogen atom
  • R Xb , R Xc and R Xd are groups of the formula (3)
  • R X11 , R X12 , R X13 , R X21 , R X22 , and R X23 are preferably a hydrogen atom.
  • R Xb , R Xc and R Xd are the same.
  • R Xa-d -bonded hydrogen atom has not been substituted in the non-bonded carbon atom, and, R Xa, R Xb, of R Xc, and R Xd, R Xa and R Xb is a hydrogen atom and R Xc and R Xd are groups of the formula (3), or (iii) the hydrogen atom bonded to the R Xa-d non-bonded carbon atom is not substituted, and R Xa , R Among Xb , R Xc , and R Xd , R Xa is a hydrogen atom and R Xb , R Xc , and R Xd are groups of the formula (3), or (iva) R Xa-d is bonded to a non-bonded carbon atom.
  • the bonded hydrogen atoms are not substituted and all of R Xa , R Xb , R Xc , and R Xd can be groups of formula (3).
  • X ii represents a divalent group obtained by removing two hydrogen atoms from a hydrocarbon ring, or a formula (2 g -ia):
  • R 1 , R 2 , R 3 , m, and n are the same as described above.
  • the epoxy resin represented by these is preferably included. Note that R 1 , R 2 , R 3 , m, and n may all be the same or different, and are preferably the same.
  • X ii preferably cyclohexane-1,4-diyl group, a 1,4-phenylene group, more preferably a 1,4-phenylene group.
  • a group in which Y is a bond, a dimethylmethylene group, an oxygen atom, or —SO 2 — is particularly preferable.
  • X ii among them preferably a cyclohexane-1,4-diyl group, a 1,4-phenylene group, the formula (2 g -iia ') can be mentioned, more preferably a 1,4-phenylene group.
  • m is the same 0, 1, 2, 3, or 4 (particularly preferably, m is the same 0 or 4) and n is the same 0 (ie, R 3 is a ring
  • X ii is a divalent group obtained by removing two hydrogen atoms from a hydrocarbon ring (particularly preferably a benzene ring), and R 1 is the same and has 1 to 3 carbon atoms.
  • a group of 2 to 6 carbon atoms in which R 2 is the same and one carbon atom which is not directly bonded to any of a silicon atom and a 3- to 6-membered ring or an epoxy ring may be substituted with an oxygen atom
  • An epoxy resin represented by showing each group can be more preferably used in the present invention.
  • X iii is a trivalent group obtained by removing three hydrogen atoms from a hydrocarbon ring, or a compound represented by the formula (2 g -iii):
  • R 1 , R 2 , R 3 , m, and n are the same as described above.
  • the epoxy resin represented by these is preferably included. Note that R 1 , R 2 , R 3 , m, and n may all be the same or different, and are preferably the same.
  • the trivalent group represented by X iii is preferably the following group:
  • a group in which Y is a bond, a dimethylmethylene group, an oxygen atom, or —SO 2 — is particularly preferable.
  • m is the same 0, 1, 2, 3, or 4 (particularly preferably, m is the same 0 or 4), and n is the same 0 (ie, R 3 represents a ring X iii is a trivalent group obtained by removing three hydrogen atoms from a hydrocarbon ring (particularly preferably a benzene ring), and R 1 is the same and has 1 to 3 carbon atoms.
  • a group of 2 to 6 carbon atoms in which R 2 is the same and one carbon atom which is not directly bonded to any of a silicon atom and a 3- to 6-membered ring or an epoxy ring may be substituted with an oxygen atom
  • An epoxy resin represented by showing each group can be more preferably used in the present invention.
  • X iv represents a tetravalent group represented by the above (1 ′) and a hydrogen atom bonded to an R Xa-d non-bonded carbon atom in the X ring is not substituted, R 1 , R 2 , R 3 , m, and n are the same as described above.
  • the epoxy resin represented by these is included. Note that R 1 , R 2 , R 3 , m, and n may all be the same or different, and are preferably the same.
  • the tetravalent group represented by X iv is preferably the following group:
  • the tetravalent group represented by X iv is preferably a tetravalent group represented by the formula (2 g ), wherein a hydrogen atom bonded to an R Xa-d non-bonded carbon atom is not substituted.
  • a hydrogen atom bonded to an R Xa-d non-bonded carbon atom is not substituted.
  • a group in which Y is a bond, a dimethylmethylene group, an oxygen atom, or —SO 2 — is particularly preferable.
  • m is the same 0, 1, 2, 3, or 4 (particularly preferably, m is the same 0 or 4) and n is the same 0 (ie, R 3 is a ring X iv is a tetravalent group obtained by removing four hydrogen atoms from a hydrocarbon ring (particularly preferably a benzene ring), and R 1 is the same and has 1 to 3 carbon atoms.
  • a group of 2 to 6 carbon atoms in which R 2 is the same and one carbon atom which is not directly bonded to any of a silicon atom and a 3- to 6-membered ring or an epoxy ring may be substituted with an oxygen atom
  • An epoxy resin represented by showing each group can be more preferably used in the present invention.
  • epoxy resins represented by the formula (1) More preferable examples include, for example, the formula (1-IIa):
  • X ii is a 1,4-phenylene group or a group represented by the formula (2 g- ia ′) (preferably a 1,4-phenylene group).
  • R 1 is the same or different (preferably the same) and is an alkyl group having 1 to 3 carbon atoms (particularly a methyl group), and
  • R 2 is the same or different (preferably the same) an alkylene having 2 to 6 carbon atoms Group (*) — (CH 2 ) 2 —O—CH 2 —, (*) — (CH 2 ) 3 —O—CH 2 —, (*) — (CH 2 ) 3 —O— (CH 2 )
  • a compound which is 2- or (*)-(CH 2 ) 5 -O- (CH 2 ) 4- is preferred.
  • the above same, (*) indicates the side bonded to the silicon atoms of R 2.
  • the epoxy resins represented by the above formula (1-IIa) more preferred are those represented by the formula (1-IIa
  • R 1 and X ii are the same as above).
  • the epoxy resin represented by these can be illustrated. Note that R 1 may be the same or different, and is preferably the same.
  • R 1 is the same or different (preferably the same) and is an alkyl group having 1 to 3 carbon atoms (particularly a methyl group), and X ii is 1, More preferred is a 4-phenylene group or a group represented by the formula (2 g -ia ′).
  • epoxy resins represented by the formula (1) more preferable examples include, for example, the formula (1-IIb):
  • R 1 , R 2 , R 3 , X ii , and n are the same as above.
  • the epoxy resin represented by these can also be mentioned. Note that R 1 , R 2 , R 3 , and n may all be the same or different, and are preferably the same.
  • X ii is a 1,4-phenylene group or a group represented by the formula (2 g -ia ′) (preferably a 1,4-phenylene group), and R 1 is the same or different.
  • n is both 0 (that is, the ring is not substituted with R 3 ), and R 2 is the same or different ( More preferably, it is the same and is an alkylene group having 2 to 6 carbon atoms (preferably a dimethylene group: — (CH 2 ) 2 —).
  • epoxy resins represented by the formula (1) more preferable examples include, for example, the formula (1-IIIa):
  • R 1 , R 2 , R 3 , X iii and n are the same as above
  • the epoxy resin represented by these can also be mentioned. Note that R 1 , R 2 , R 3 , and n may all be the same or different, and are preferably the same.
  • X iii is
  • R 1 is the same or different (preferably the same) and is an alkyl group having 1 to 3 carbon atoms (particularly a methyl group), and both n are 0 (That is, the ring is not substituted with R 3 ), and R 2 is the same or different (preferably the same) and is an alkylene group having 2 to 6 carbon atoms (preferably a dimethylene group: — (CH 2 ) 2 —) Is more preferable.
  • the epoxy resin represented by the formula (1) can be used alone or in combination of two or more.
  • the epoxy resin represented by the formula (1) can be produced based on or according to a known method, for example, based on or according to the description of Patent Document 2 (UK Patent No. 1123960). Also, for example, an epoxy resin represented by the formula (1-ia) can be produced by a reaction represented by the following reaction formula.
  • R 2A is an alkenyl group having 2 to 18 carbon atoms, and in this group, some carbon atoms are substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom.
  • R 1 , R 2 , R 3 , and X ii are the same as above.
  • the alkenyl group having 2 to 18 carbon atoms represented by R 2A is a linear or branched alkenyl group, and is preferably a straight chain. Specific examples include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a norbornenyl group, and a cyclohexenyl group.
  • alkenyl group having 2 to 10 carbon atoms is preferred, an alkenyl group having 2 to 8 carbon atoms is more preferred, an alkenyl group having 2 to 6 carbon atoms is more preferred, and a vinyl group, allyl group or It is a butenyl group.
  • the alkenyl group is preferably an ⁇ -alkenyl group.
  • alkenyl groups having 2 to 18 carbon atoms some carbon atoms may be substituted with at least one atom (preferably an oxygen atom) selected from the group consisting of an oxygen atom and a nitrogen atom.
  • the some carbon atoms are preferably carbon atoms not directly bonded to the epoxy ring.
  • the part of carbon atoms that may be substituted is 1 or a plurality of (for example, 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom.
  • Examples of the group include 2 to 9 alkenyl-O-carbon having 1 to 8 carbon atoms, preferably 2 to 4 alkenyl-O carbon atoms having 1 to 3 carbon atoms, more preferably 2 to 3 carbon atoms.
  • Examples thereof include 4 alkenyl-O-alkylene having 1 to 2 carbon atoms, particularly preferably 3 alkenyl-O—CH 2 —.
  • the epoxy resin represented by the formula (1-ia) can be produced by subjecting the compound represented by the formula (5-ia) and the compound represented by the formula (6) to a hydrosilylation reaction.
  • the hydrosilylation reaction can usually be carried out in the presence of a catalyst, in the presence or absence of a solvent. Further, in place of the compound represented by the formula (5-ia), the formula (5-iii):
  • X i represents a monovalent group obtained by removing one hydrogen atom from a hydrocarbon ring
  • R 1 is the same as above.
  • X i to X iv are each a monovalent group obtained by removing one hydrogen atom from the X ring, and 2 obtained by removing two hydrogen atoms from the X ring.
  • the catalyst used in the hydrosilylation reaction may be a known catalyst such as platinum catalyst such as platinum carbon, chloroplatinic acid, platinum olefin complex, platinum alkenylsiloxane complex, platinum carbonyl complex, etc .; Fin) rhodium and other rhodium catalysts; and iridium catalysts such as bis (cyclooctadienyl) dichloroiridium.
  • platinum catalyst such as platinum carbon, chloroplatinic acid, platinum olefin complex, platinum alkenylsiloxane complex, platinum carbonyl complex, etc .
  • Fin rhodium and other rhodium catalysts
  • iridium catalysts such as bis (cyclooctadienyl) dichloroiridium.
  • the above catalyst may be in the form of a solvate (for example, hydrate, alcohol solvate, etc.). In use, the catalyst may be dissolved in an alcohol (for example, ethanol) and used in the form of
  • the amount of the catalyst used may be an effective amount as a catalyst.
  • the hydrosilylation reaction proceeds without using a solvent, but the reaction can be performed under mild conditions by using a solvent.
  • the solvent include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane and octane; ether solvents such as tetrahydrofuran and dioxane; alcohol solvents such as ethanol and isopropanol; These may be used alone or in combination of two or more.
  • the amount of the compound represented by the formula (6) is, for example, Si— in the compound represented by the formula (5-ia), (5-ia), (5-iii), or (5-iva).
  • the amount is usually 0.5 to 2 mol, preferably 0.6 to 1.5 mol, more preferably 0.8 to 1.2 mol, relative to 1 mol of the H group.
  • the reaction temperature is usually 0 ° C. to 150 ° C., preferably 10 ° C. to 120 ° C., and the reaction time is usually about 1 hour to 24 hours.
  • the epoxy resin represented by the formula (1) can be obtained by using a known isolation method such as distilling off the solvent from the reaction solution.
  • the active ester compound used in the present invention is a compound having an ester group (preferably an ester group having high reaction activity).
  • an ester group having high reaction activity preferably an ester group having high reaction activity.
  • a compound having two or more ester groups in one molecule is preferable.
  • compounds having two or more ester groups in one molecule such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds are preferable.
  • the active ester compound is a compound obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound (that is, at least selected from the group consisting of a carboxylic acid compound and a thiocarboxylic acid compound).
  • 1 type and the condensate of at least 1 sort (s) selected from the group which consists of a hydroxy compound and a thiol compound) are preferable.
  • a condensate obtained from a carboxylic acid compound and a hydroxy compound is preferred, and a condensate obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred.
  • a condensate (active ester compound) can be preferably used as an epoxy resin curing agent.
  • carboxylic acid compound examples include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
  • Examples of the thiocarboxylic acid compound include thioacetic acid and thiobenzoic acid.
  • hydroxy compound examples include a phenol compound or a naphthol compound.
  • Examples of the thiol compound include benzenedithiol and triazinedithiol.
  • active ester compound for example, active ester compounds disclosed in JP2009-235165A, JP2004-277460A, or WO2013 / 061688 can be used. It is more preferable to use an active ester compound described in JP-A-2009-235165.
  • the contents described in the specifications and / or drawings of JP 2009-235165 A, JP 2004-277460 A, and WO 2013/061688 are incorporated herein by reference.
  • an ester compound containing a dicyclopentadienyl diphenol structure is particularly preferable.
  • R 4 represents a phenyl group or a naphthyl group, y represents an integer of 0 or 1, and z represents an average of repeating units of 0.05 to 2.5).
  • R 4 is preferably a naphthyl group.
  • y is preferably 0.
  • z is preferably 0.25 to 1.5. From the viewpoint of electrical characteristics and heat resistance, it is more preferable that R 4 is a naphthyl group, y is 0, and z is 0.25 to 1.5.
  • an active ester compound a polyester comprising an aromatic polyvalent carboxylic acid residue and an aromatic polyvalent hydroxy compound residue having an aryloxycarbonyl group at a molecular chain end, the aromatic polyvalent hydroxy compound
  • the residue is of formula (8a):
  • A is the same or different and represents an alkyl group having 1, 2, 3 or 4 carbon atoms, an alkoxy group having 1, 2, 3 or 4 carbon atoms, or a halogen atom, and a is 0, 1, 2, 3 or 4
  • the aryloxycarbonyl group is represented by the formula (8c-1):
  • P is the same or different and represents an alkyl group having 1, 2, 3 or 4 carbon atoms, an alkoxy group having 1, 2, 3 or 4 carbon atoms, a nitro group, or a halogen atom, and p is 0. , 1, 2, 3, 4 or 5), or a group represented by formula (8c-2):
  • U and T are the same or different and each represents an alkyl group having 1, 2, 3 or 4 carbon atoms, an alkoxy group having 1, 2, 3 or 4 carbon atoms, a nitro group, or a halogen atom; Represents 0, 1, 2, or 3, and t represents 0, 1, 2, 3, or 4.), or a group represented by formula (8c-3):
  • Q and R are the same or different and each represents an alkyl group having 1, 2, 3 or 4 carbon atoms, an alkoxy group having 1, 2, 3 or 4 carbon atoms, a nitro group, or a halogen atom; Represents 0, 1, 2, 3, or 4, and r represents 0, 1, 2, 3, 4, or 5.
  • Z represents a single bond, —O—, —CO—, —CH 2 —, — A polyester represented by C (CH 3 ) 2 — or —SO 2 — is also preferred.
  • alkyl group having 1, 2, 3 or 4 carbon atoms examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group.
  • 1, 2, 3 or 4 alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and t-butoxy.
  • polyesters include at least one kind of an acid halide of an aromatic polyvalent carboxylic acid, at least one kind of an aromatic monohydroxy compound, and an aromatic polyvalent hydroxy compound described in Table 1 below.
  • polyesters obtained by reacting dicyclopentadienyl diphenol).
  • the active ester compounds can be used alone or in combination of two or more.
  • ester compounds can also be used as the active ester compound in the present invention.
  • an ester compound containing a dicyclopentadienyl diphenol structure, an acetylated product of a phenol novolak, a benzoylated product of a phenol novolak, etc. are preferable, and among them, a dicyclopentadienyl diphenol structure is included.
  • An ester compound is more preferable.
  • ester compounds containing a dicyclopentadienyl diphenol structure EXB9451, EXB9460, EXB9460S-65T, HPC-8000-65T (manufactured by DIC, active group equivalent of about 223), phenol novolac acetyl DC808 (Mitsubishi Chemical Corporation, active group equivalent of about 149) as a compound, YLH1026 (Mitsubishi Chemical Corporation, active group equivalent of about 200), YLH1030 (Mitsubishi Chemical Corporation, active group equivalent of about 201) as a benzoylated phenol novolak, YLH1048 (manufactured by Mitsubishi Chemical Corporation, active group equivalent of about 245), and the like.
  • HPC-8000-65T examples include HPC-8000-65T (manufactured by DIC, ester equivalent of about 223 g / eq).
  • HPC-8000-65T is known to cure an epoxy resin by the following reaction (in the following formula, HPC-8000-65T is R ′′ —CO—O—R ′ ′′). Represented).
  • the blending ratio of the active ester compound in the epoxy resin composition according to the present invention is not particularly limited as long as the effect of the present invention can be exhibited.
  • the mixing ratio of the epoxy resin and the active ester compound is preferably such that, for example, the equivalent ratio of the epoxy group of the epoxy resin to the ester group of the active ester compound (epoxy group / ester group) is 0.2 to 3. 0.5 to 1.5 is more preferable, and 0.8 to 1.2 is more preferable. When the equivalent ratio is 3 or less, the dielectric properties can be further improved. Further, when the equivalent ratio is 0.2 or more, heat resistance is preferably improved.
  • the active ester compound is based on 100 parts by mass of the epoxy resin in the epoxy resin composition.
  • 50 to 200 parts by mass, preferably 75 to 175 parts by mass, and more preferably 80 to 150 parts by mass can be blended.
  • the epoxy resin represented by the formula (1) can be used alone or in combination of two or more.
  • an active ester compound can also be used individually or in combination of 2 or more types.
  • the epoxy resin composition of the present invention may further contain a curing catalyst.
  • a curing catalyst it is not particularly limited as long as it promotes the crosslinking reaction of the epoxy resin represented by the formula (1), or promotes the crosslinking reaction between the epoxy resin represented by the formula (1) and the active ester compound.
  • curing catalyst examples include imidazole compounds, dicyandiamides, tertiary amines, phosphorus compounds, Lewis acid compounds, and cationic polymerization initiators.
  • the epoxy resin composition of the present invention may contain an epoxy resin other than the epoxy resin represented by the formula (1) as long as the effects of the present invention are not impaired.
  • the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated epoxy resin, triglycidyl isocyanurate, hydrogenated Bisphenol A type epoxy resins, aliphatic epoxy resins, glycidyl ether type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins, dicyclo type epoxy resins, naphthalene type epoxy resins and the like can be used. These epoxy resins may be used alone or in combination of two or more.
  • the blending ratio of the epoxy resin represented by formula (1) and the epoxy resin other than the epoxy resin represented by formula (1) is The mass ratio is, for example, 100: 0 to 20:80, preferably 100: 0 to 30:70, and more preferably 100: 0 to 40:60.
  • the epoxy resin composition of the present invention may contain a filler, a curing agent, a thermoplastic resin, an additive, and the like as necessary within a range that does not impair the object and effect of the present invention.
  • the filler considering the fluidity, heat resistance, low thermal expansion property, mechanical properties, hardness, scratch resistance, adhesiveness, etc. required for the composition and cured product, the filler alone or A plurality of types can be mixed and used.
  • silica more specifically, crystalline silica, fused silica, spherical fused silica, etc.
  • titanium oxide zirconium oxide, zinc oxide, tin oxide, silicon nitride, silicon carbide, boron nitride, calcium carbonate, calcium silicate
  • examples include inorganic compounds such as potassium acid, aluminum nitride, indium oxide, alumina, antimony oxide, cerium oxide, magnesium oxide, iron oxide, and tin-doped indium oxide (ITO).
  • metals such as gold
  • minerals such as montmorillonite, talc, mica, boehmite, kaolin, smectite, zonolite, verculite, and sericite can be mentioned.
  • Other fillers include carbon compounds such as carbon black, acetylene black, ketjen black and carbon nanotubes; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; various glasses such as glass beads, glass flakes and glass balloons Can be mentioned. Further, the filler may be used as it is, or a filler dispersed in a resin may be used.
  • curing agent examples include amine curing agents, amide curing agents, acid anhydride curing agents, phenol curing agents, mercaptan curing agents, isocyanate curing agents, and cyanate ester curing agents.
  • curing agent may be used independently, and can be used properly according to the characteristic to request
  • amine curing agents include chain aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; isophoronediamine, benzenediamine, bis (4-aminocyclohexyl) methane, and bis (aminomethyl) cyclohexane.
  • Alicyclic amines such as diaminodicyclohexylmethane; aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, diethyltoluenediamine, diaminodiethyldiphenylmethane; benzyldimethylamine, triethylenediamine, piperidine, 2- (dimethylaminomethyl) phenol, 2 , 4,6-Tris (dimethylaminomethyl) phenol, DBU (1,8-diazabicyclo (5,4,0) -undecene-7), DBN (1, - diazabicyclo (4,3,0) - nonene-5), and a secondary and tertiary amines, such as.
  • amide-based curing agents examples include dicyandiamide and its derivatives, polyamide resins (polyaminoamide, etc.), and the like.
  • acid anhydride curing agents examples include aliphatic acid anhydrides such as maleic anhydride and dodecenyl succinic anhydride; aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride; methyl nadic anhydride And alicyclic acid anhydrides such as acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 4-methylhexahydrophthalic anhydride.
  • phenolic curing agents include phenol novolak resins, cresol novolak resins, biphenyl type novolak resins, triphenylmethane type phenol resins, naphthol novolak resins, phenol biphenylene resins, phenol aralkyl resins, biphenyl aralkyl type phenol resins, and modified polyphenylene ether resins. And compounds having a benzoxazine ring.
  • Examples of mercaptan curing agents include trimethylolpropane tris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), Tetraethylene glycol bis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercaptobutyrate) , Trimethylol ethane tris (3-mercaptobutyrate), polysulfide polymer and the like.
  • isocyanate curing agent examples include hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, lysine diisocyanate, isophorone diisocyanate, and norbornane diisocyanate.
  • thermoplastic resin examples include polyolefin resin, acrylic resin, phenoxy resin, polyamide resin, polyester resin, polycarbonate resin, polyurethane resin, polyarylate resin, polyphenylene ether resin, polyacetal resin, and those obtained by acid modification. Is mentioned. From the viewpoint of compatibility with the epoxy resin composition according to the present invention and heat resistance, polyolefin resins, acrylic resins, phenoxy resins, polyarylate resins, polyphenylene ether resins, and those obtained by acid modification are preferred, among these More preferred are polyolefin resins and acid-modified polyolefin resins.
  • the additive examples include an antioxidant, an inorganic phosphor, a lubricant, an ultraviolet absorber, a heat and light stabilizer, an antistatic agent, a polymerization inhibitor, an antifoaming agent, a solvent, an antiaging agent, a radical inhibitor, and an adhesive.
  • Examples include decomposing agents, pigments, metal deactivators, and physical property modifiers.
  • the epoxy resin composition of the present invention can be produced by mixing the epoxy resin represented by the formula (1) and the active ester compound and, if necessary, other components.
  • the mixing method is not particularly limited as long as it can be uniformly mixed.
  • a solvent for example, toluene, xylene, methyl ethyl ketone, acetone, cyclohexanone, methylcyclohexane, cyclohexane, etc.
  • a solvent for example, toluene, xylene, methyl ethyl ketone, acetone, cyclohexanone, methylcyclohexane, cyclohexane, etc.
  • a cured product (that is, a cured product of the epoxy resin composition) can be obtained by curing the epoxy resin composition of the present invention.
  • the curing method is not particularly limited, and can be carried out, for example, by heat curing the composition.
  • the curing temperature is usually room temperature to 300 ° C., and the curing time varies depending on the composition liquid, and can be set widely from 30 minutes to 1 week.
  • Each component in Table 2 and Table 3 is as follows. In addition, the numerical value of each component of Table 2 and Table 3 shows a mass part.
  • Epoxy resin F Bis-A type epoxy resin (grade 828) manufactured by Mitsubishi Chemical Corporation (epoxy equivalent 189 g / eq)
  • Epoxy resin G Alicyclic epoxy resin manufactured by Daicel (Celoxide 2021P; generic name is 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate) (epoxy equivalent 137 g / eq)
  • Active ester compound Active ester resin EPICLON HPC-8000-65T manufactured by DIC (toluene solution, solid content concentration 65%, ester equivalent of about 223 g / eq)
  • Curing catalyst 4-dimethylaminopyridine (DMAP) manufactured by Tokyo Chemical Industry Co., Ltd.

Abstract

Provided is an epoxy resin composition having excellent electrical characteristics (especially a low dielectric loss tangent) and being capable of achieving high adhesion to metal.　Specifically, an epoxy resin composition containing an active ester compound and an epoxy resin having a specific structure is provided.

Description

エポキシ樹脂組成物Epoxy resin composition
　本発明は、エポキシ樹脂組成物、その製造方法、及び該組成物の用途等に関する。 The present invention relates to an epoxy resin composition, a method for producing the same, a use of the composition, and the like.
　近年、電子デバイスの高性能化及び軽薄短小化に伴い、伝送信号の高周波化が進んでいる。高周波化に伴い、プリント配線板及び半導体封止材に使用する材料に対して、高周波領域での低誘電化が強く求められている。当該分野においては、エポキシ樹脂などの熱硬化性樹脂が基板材料や封止材として広く用いられている。特許文献１には特定のエポキシ樹脂と特定の活性エステル化合物とを含むエポキシ樹脂組成物が高い密着性と低誘電正接特性を有することが記載されている。 In recent years, transmission signals have become higher in frequency as electronic devices become more sophisticated and light and thin. With higher frequencies, there is a strong demand for lower dielectrics in the high-frequency region for materials used for printed wiring boards and semiconductor encapsulants. In this field, thermosetting resins such as epoxy resins are widely used as substrate materials and sealing materials. Patent Document 1 describes that an epoxy resin composition containing a specific epoxy resin and a specific active ester compound has high adhesion and low dielectric loss tangent characteristics.
特開２０１６－１１７９０４号公報JP 2016-117904 A 特開２００４－２７７４６０号公報JP 2004-277460 A 英国特許第１１２３９６０号明細書British Patent No. 1123960
　しかし、特許文献１のエポキシ樹脂組成物では、その硬化物の誘電特性は改善されてはいるものの、未だ十分とはいえない。
　そこで、本発明は、硬化した際に、優れた電気特性（特に、低誘電正接）を有し、金属への高い接着強度が達成できるエポキシ樹脂組成物を提供することを課題とする。 However, although the epoxy resin composition of Patent Document 1 has improved the dielectric properties of the cured product, it is still not sufficient.
Then, this invention makes it a subject to provide the epoxy resin composition which has the outstanding electrical property (especially low dielectric loss tangent), and can achieve the high adhesive strength to a metal, when hardened | cured.
　　本発明者は、上記の課題を解決するべく鋭意研究を行った結果、ケイ素原子を含む特定のエポキシ樹脂と活性エステル化合物とを含有するエポキシ樹脂組成物が、優れた低誘電特性を有することを見出した。この知見に基づいてさらに研究を重ね本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an epoxy resin composition containing a specific epoxy resin containing a silicon atom and an active ester compound has excellent low dielectric properties. I found it. Based on this knowledge, further studies have been made and the present invention has been completed.
　　本発明は、以下の項に記載の主題を包含する。
　項１．
　式（１）： The present invention encompasses the subject matter described in the following sections.
Item 1.
Formula (1):
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　（式中、Ｘ環は
　飽和炭化水素環又は不飽和炭化水素環、あるいは
　飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合又は２個連結した構造を有する環であり、
　ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、同一又は異なって、水素原子、低級アルキル基、低級アルコキシ基、低級アルケニル基、ハロゲン原子、又は式（３）： (In the formula, ring X is a saturated hydrocarbon ring or unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed or connected,
R Xa , R Xb , R Xc , and R Xd are the same or different and are a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyl group, a halogen atom, or formula (3):
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　（式中、Ｒ１は同一又は異なって、炭素数１～１８のアルキル基、炭素数２～９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基を示し、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
　　Ｒ２は、炭素数１～１８のアルキレン基を示し、この基は、ケイ素原子に直接結合した炭素原子を除く一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
　　Ｒ３は同一又は異なって、炭素数１～１８のアルキル基、炭素数２～９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基を示し、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
　ｍは０～６の整数を示し、
　ｎは０～３の整数を示す。）で表される基を示し、
　但し、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄのうち、少なくとも１つは式（３）で表される基であり、
　Ｘ環を構成する炭化水素環を構成する炭素原子であって且つＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄが結合していない炭素原子に結合した水素原子が、低級アルキル基、低級アルコキシ基、低級アルケニル基、又はハロゲン原子で置換されていてもよい。）
　で表されるエポキシ樹脂と活性エステル化合物とを含有するエポキシ樹脂組成物。
　項２．
　前記飽和炭化水素環及び／又は不飽和炭化水素環が２個連結した構造を有する環が、
　式（２）： (In the formula, R 1 is the same or different and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. The carbon atom may be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom;
R 2 represents an alkylene group having 1 to 18 carbon atoms, and this group is at least one selected from the group consisting of oxygen atoms and nitrogen atoms, with some carbon atoms excluding carbon atoms directly bonded to silicon atoms. May be substituted with
R 3 s are the same or different and each represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and these groups have a part of carbon atoms, May be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom,
m represents an integer of 0 to 6,
n represents an integer of 0 to 3. )
However, at least one of R Xa , R Xb , R Xc , and R Xd is a group represented by the formula (3),
A hydrogen atom bonded to a carbon atom constituting a hydrocarbon ring constituting the X ring and to which R Xa , R Xb , R Xc , and R Xd are not bonded is a lower alkyl group or a lower alkoxy group , A lower alkenyl group, or a halogen atom. )
The epoxy resin composition containing the epoxy resin represented by these, and an active ester compound.
Item 2.
A ring having a structure in which two saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are connected,
Formula (2):
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　（式中、Ｘ１環及びＸ２環は、同一又は異なって、飽和炭化水素環又は不飽和炭化水素環を示し、Ｙは、結合手、炭素数１～４のアルキル基で置換されていてもよい炭素数１～６のアルキレン基、酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、－ＳＯ－、又は－ＳＯ２－を示す。）で表される環である、項１に記載のエポキシ樹脂組成物。
　項３．
　前記飽和炭化水素環が炭素数４～８の飽和炭化水素環であり、
　前記不飽和炭化水素環が炭素数４～８の不飽和炭化水素環である、
　項１又は２に記載のエポキシ樹脂組成物。
　項４．
式（１－ｉｉａ）： (Wherein, ring X 1 and ring X 2 are the same or different and each represents a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, and Y is a bond, substituted with an alkyl group having 1 to 4 carbon atoms. Or a ring represented by an alkylene group having 1 to 6 carbon atoms, an oxygen atom (—O—), a sulfur atom (—S—), —SO—, or —SO 2 —). The epoxy resin composition described in 1.
Item 3.
The saturated hydrocarbon ring is a saturated hydrocarbon ring having 4 to 8 carbon atoms;
The unsaturated hydrocarbon ring is an unsaturated hydrocarbon ring having 4 to 8 carbon atoms;
Item 3. The epoxy resin composition according to Item 1 or 2.
Item 4.
Formula (1-ia):
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
（式中、Ｘｉｉは、飽和炭化水素環若しくは不飽和炭化水素環、又は飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合した構造を有する環、から２個の水素原子を除いて得られる２価の基、あるいは式（２ｇ－ｉｉａ）： ( Wherein X ii represents a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed, to two hydrogen atoms A divalent group obtained by removing or a formula (2 g -ia):
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
（式中、Ｙは、結合手、炭素数１～４のアルキル基で置換されていてもよい炭素数１～６のアルキレン基、酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、－ＳＯ－、又は－ＳＯ２－を示す。）で表される２価の基を示し、
Ｒ１は同一又は異なって、炭素数１～１８のアルキル基、炭素数２～９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基を示し、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
　Ｒ２は同一又は異なって、炭素数１～１８のアルキレン基を示し、この基は、ケイ素原子に直接結合した炭素原子を除く一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
　Ｒ３は同一又は異なって、炭素数１～１８のアルキル基、炭素数２～９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基を示し、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
ｍは０～６の整数を示し、
ｎは０～３の整数を示す。）
で表されるエポキシ樹脂、並びに
式（１－ｉｉｉａ）： (Wherein Y represents a bond, an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, an oxygen atom (—O—), a sulfur atom (—S—), -SO- or -SO 2- )).
R 1 s are the same or different and each represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and these groups have a part of carbon atoms, May be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom,
R 2 is the same or different and represents an alkylene group having 1 to 18 carbon atoms, and this group is selected from the group consisting of oxygen atoms and nitrogen atoms, with some carbon atoms excluding carbon atoms directly bonded to silicon atoms. Optionally substituted with at least one atom
R 3 s are the same or different and each represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and these groups have a part of carbon atoms, May be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom,
m represents an integer of 0 to 6,
n represents an integer of 0 to 3. )
And an epoxy resin represented by the formula (1-iiia):
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
（式中、Ｘｉｉｉは、飽和炭化水素環若しくは不飽和炭化水素環、又は飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合した構造を有する環、から３個の水素原子を除いて得られる３価の基、又は式（２ｇ－ｉｉｉａ）： (In the formula, X iii is a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed, to 3 hydrogen atoms A trivalent group obtained by removing or a formula (2 g -iiia):
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
（式中、Ｙは、前記に同じ。）で表される３価の基を示し、
Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは前記に同じ。）
で表されるエポキシ樹脂
からなる群より選択される少なくとも１種のエポキシ樹脂と活性エステル化合物とを含有する、項１に記載のエポキシ樹脂組成物。
項５．
活性エステル化合物が、エステル基を１分子中に２個以上有する化合物である、項１～４のいずれかに記載のエポキシ樹脂組成物。
項６．
活性エステル化合物が、カルボン酸化合物及びチオカルボン酸化合物からなる群より選択される少なくとも１種と、ヒドロキシ化合物及びチオール化合物からなる群より選択される少なくとも１種との、縮合物である、項１～４のいずれかに記載のエポキシ樹脂組成物。
項７．
活性エステル化合物が、ジシクロペンタジエニルジフェノール構造を含むエステル化合物である、項１～４のいずれかに記載のエポキシ樹脂組成物。
項８．
項１～７のいずれかに記載のエポキシ樹脂組成物の硬化物。
項９．
項１～７のいずれかに記載のエポキシ樹脂組成物又は項８に記載の硬化物が用いられている半導体封止体、液状封止材、ポッティング材、シール材、層間絶縁膜、接着層、カバーレイフィルム、電磁波シールドフィルム、プリント基板材料又は複合材料。
項１０．
半導体封止体、液状封止材、ポッティング材、シール材、層間絶縁膜、接着層、カバーレイフィルム、電磁波シールドフィルム、プリント基板材料又は複合材料の用途に用いられる項１～７のいずれかに記載のエポキシ樹脂組成物又は項８に記載の硬化物。
項１１．
半導体封止体、液状封止材、ポッティング材、シール材、層間絶縁膜、接着層、カバーレイフィルム、電磁波シールドフィルム、プリント基板材料又は複合材料を製造するための項１～７のいずれかに記載のエポキシ樹脂組成物又は項８に記載の硬化物の使用。 (Wherein Y represents the same as described above),
R 1 , R 2 , R 3 , m, and n are the same as described above. )
Item 2. The epoxy resin composition according to Item 1, comprising at least one epoxy resin selected from the group consisting of epoxy resins represented by the formula (1) and an active ester compound.
Item 5.
Item 5. The epoxy resin composition according to any one of Items 1 to 4, wherein the active ester compound is a compound having two or more ester groups in one molecule.
Item 6.
Item 1. The active ester compound is a condensate of at least one selected from the group consisting of carboxylic acid compounds and thiocarboxylic acid compounds and at least one selected from the group consisting of hydroxy compounds and thiol compounds. 4. The epoxy resin composition according to any one of 4 above.
Item 7.
Item 5. The epoxy resin composition according to any one of Items 1 to 4, wherein the active ester compound is an ester compound containing a dicyclopentadienyl diphenol structure.
Item 8.
Item 8. A cured product of the epoxy resin composition according to any one of Items 1 to 7.
Item 9.
A semiconductor encapsulant, a liquid encapsulant, a potting material, a sealing material, an interlayer insulating film, an adhesive layer, wherein the epoxy resin composition according to any one of Items 1 to 7 or the cured product according to Item 8 is used, Coverlay film, electromagnetic shielding film, printed circuit board material or composite material.
Item 10.
Any one of Items 1 to 7 used for a semiconductor encapsulant, a liquid encapsulant, a potting material, a sealant, an interlayer insulating film, an adhesive layer, a cover lay film, an electromagnetic shielding film, a printed circuit board material, or a composite material Item 9. The epoxy resin composition according to Item 8 or the cured product according to Item 8.
Item 11.
Item 1 to 7 for producing a semiconductor encapsulant, liquid encapsulant, potting material, sealing material, interlayer insulating film, adhesive layer, coverlay film, electromagnetic wave shielding film, printed circuit board material or composite material Use of the epoxy resin composition according to Item 8 or the cured product according to Item 8.
　本発明のエポキシ樹脂組成物は、その硬化物が優れた電気特性、金属への高い接着強度を有している。そのため、本発明のエポキシ樹脂組成物は、例えば、半導体封止体、液状封止材、ポッティング材、シール材、層間絶縁膜、接着層、カバーレイフィルム、電磁波シールドフィルム、プリント基板材料、複合材料等の広範な用途に好適に用いることができる。 In the epoxy resin composition of the present invention, the cured product has excellent electrical characteristics and high adhesive strength to metal. Therefore, the epoxy resin composition of the present invention includes, for example, a semiconductor sealing body, a liquid sealing material, a potting material, a sealing material, an interlayer insulating film, an adhesive layer, a cover lay film, an electromagnetic wave shielding film, a printed board material, and a composite material. It can be suitably used for a wide range of uses.
　以下、本発明の各実施形態について、さらに詳細に説明する。 Hereinafter, each embodiment of the present invention will be described in more detail.
　本発明に包含されるエポキシ樹脂組成物は、式（１）： The epoxy resin composition included in the present invention has the formula (1):
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
で表されるエポキシ樹脂および活性エステル化合物を含有する。 And an active ester compound.
　式（１）において、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、同一又は異なって、水素原子、低級アルキル基、低級アルコキシ基、低級アルケニル基、ハロゲン原子、又は式（３）： In the formula (1), R Xa , R Xb , R Xc , and R Xd are the same or different and are a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyl group, a halogen atom, or the formula (3):
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
で表される基（以下「式（３）の基」ということがある）を示す。なお、以下、低級アルキル基、低級アルコキシ基、及び低級アルケニル基をまとめて、「低級炭素置換基」ということがある。本発明においては、低級炭素置換基の中でも、低級アルキル基又は低級アルコキシ基がより好ましい。 (Hereinafter sometimes referred to as “group of formula (3)”). Hereinafter, the lower alkyl group, the lower alkoxy group, and the lower alkenyl group may be collectively referred to as “lower carbon substituent”. In the present invention, among the lower carbon substituents, a lower alkyl group or a lower alkoxy group is more preferable.
　但し、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄのうち、少なくとも１つは式（３）の基である。言い換えれば、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、３つが水素原子若しくはハロゲン原子又は低級炭素置換基で１つが式（３）の基であるか、２つが水素原子若しくはハロゲン原子又は低級炭素置換基で２つが式（３）の基であるか、１つが水素原子若しくはハロゲン原子又は低級炭素置換基で３つが式（３）の基であるか、あるいは全てが式（３）の基である。より具体的には、例えば、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄのうち、（ｉ）ＲＸａ、ＲＸｂ及びＲＸｃが水素原子若しくはハロゲン原子又は低級炭素置換基でＲＸｄが式（３）の基であるか、（ｉｉ）ＲＸａ及びＲＸｂが水素原子若しくはハロゲン原子又は低級炭素置換基でＲＸｃ及びＲＸｄが式（３）の基であるか、（ｉｉｉ）ＲＸａが水素原子若しくはハロゲン原子又は低級炭素置換基でＲＸｂ、ＲＸｃ、及びＲＸｄが式（３）の基であるか、あるいは（ｉｖ）ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄの全てが式（３）の基であり得る。なお、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄのうち、式（３）の基でないものは、水素原子又は低級炭素置換基であることが、より好ましい。 However, at least one of R Xa , R Xb , R Xc , and R Xd is a group of the formula (3). In other words, R Xa , R Xb , R Xc , and R Xd are three hydrogen atoms or halogen atoms or lower carbon substituents and one is a group of formula (3), or two are hydrogen atoms or halogen atoms or Two of the lower carbon substituents are groups of formula (3), one is a hydrogen atom or halogen atom or lower carbon substituent and three are groups of formula (3), or all are of formula (3) It is a group. More specifically, for example, among R Xa , R Xb , R Xc , and R Xd , (i) R Xa , R Xb, and R Xc are a hydrogen atom, a halogen atom, or a lower carbon substituent, and R Xd is a formula (Ii) R Xa and R Xb are a hydrogen atom, a halogen atom or a lower carbon substituent, and R Xc and R Xd are a group of formula (3), or (iii) R Xa Is a hydrogen atom or a halogen atom or a lower carbon substituent, and R Xb , R Xc , and R Xd are groups of the formula (3), or (iv) all of R Xa , R Xb , R Xc , and R Xd Can be a group of formula (3). Of R Xa , R Xb , R Xc , and R Xd , those that are not the group of formula (3) are more preferably a hydrogen atom or a lower carbon substituent.
　式（１）において、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、同一又は異なってよい。従って、（ｉ）ＲＸａ、ＲＸｂ及びＲＸｃが水素原子若しくはハロゲン原子又は低級炭素置換基でＲＸｄが式（３）の基である場合は、ＲＸａ、ＲＸｂ及びＲＸｃが同一又は異なってよく、（ｉｉ）ＲＸａ及びＲＸｂが水素原子若しくはハロゲン原子又は低級炭素置換基でＲＸｃ及びＲＸｄが式（３）の基である場合は、ＲＸａ及びＲＸｂが同一又は異なってよく、ＲＸｃ及びＲＸｄも同一又は異なってよく、（ｉｉｉ）ＲＸａが水素原子若しくはハロゲン原子又は低級炭素置換基でＲＸｂ、ＲＸｃ、及びＲＸｄが式（３）の基である場合は、ＲＸｂ、ＲＸｃ、及びＲＸｄが同一又は異なってよく、（ｉｖ）ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄの全てが式（３）の基である場合は、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄが同一又は異なってよい。なお、これらいずれの場合においても、式（３）の基が同一であることが好ましい。 In the formula (1), R Xa , R Xb , R Xc , and R Xd may be the same or different. Therefore, (i) when R Xa , R Xb and R Xc are a hydrogen atom, a halogen atom or a lower carbon substituent and R Xd is a group of formula (3), R Xa , R Xb and R Xc are the same or (Ii) when R Xa and R Xb are a hydrogen atom, a halogen atom or a lower carbon substituent and R Xc and R Xd are a group of formula (3), R Xa and R Xb are the same or different R Xc and R Xd may be the same or different, and (iii) R Xa is a hydrogen atom, a halogen atom, or a lower carbon substituent, and R Xb , R Xc , and R Xd are a group of the formula (3) If, R Xb, R Xc, and R Xd may be the same or different and, (iv) if all the R Xa, R Xb, R Xc , and R Xd is a group of formula (3) is, R Xa , R Xb, R Xc, Fine R Xd may be the same or different. In any of these cases, the groups of the formula (3) are preferably the same.
　また、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄのうち、２又は３個がハロゲン原子又は低級炭素置換基である場合には、これらのハロゲン原子又は低級炭素置換基も同一又は異なってよい。この場合は、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄのうち、２又は３個が、同一の低級炭素置換基であることがさらに好ましい。 In addition, when 2 or 3 of R Xa , R Xb , R Xc , and R Xd are halogen atoms or lower carbon substituents, these halogen atoms or lower carbon substituents may be the same or different. . In this case, it is more preferable that 2 or 3 of R Xa , R Xb , R Xc , and R Xd are the same lower carbon substituent.
　本明細書において、低級炭素置換基とは、低級アルキル基、低級アルコキシ基、又は低級アルケニル基をいう。ここでの低級とは、炭素数１～６（１、２、３、４、５、又は６）を意味する。低級炭素置換基のうち、好ましくは低級アルキル基又は低級アルコキシ基である。低級アルキル基としては、具体的にはメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基等が好ましく例示できる。低級アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基等が好ましく例示できる。 In the present specification, the lower carbon substituent refers to a lower alkyl group, a lower alkoxy group, or a lower alkenyl group. Here, “lower” means 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6). Of the lower carbon substituents, a lower alkyl group or a lower alkoxy group is preferred. Specific examples of the lower alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Preferred examples of the lower alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group.
　また、本明細書において、ハロゲン原子はフッ素原子、塩素原子、臭素原子、又はヨウ素原子であり、好ましくはフッ素原子、塩素原子、又は臭素原子であり、より好ましくはフッ素原子又は臭素原子である。 In this specification, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a fluorine atom, a chlorine atom, or a bromine atom, and more preferably a fluorine atom or a bromine atom.
　式（１）において、Ｘ環は飽和炭化水素環又は不飽和炭化水素環、あるいは飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合又は２個連結した構造を有する環を表す。　本明細書において、飽和炭化水素環としては、例えば炭素数４～８（４、５、６、７、又は８）の飽和炭化水素環が好ましく、シクロペンタン環、シクロヘキサン環等が特に好ましい。また、本明細書において、不飽和炭化水素環としては、例えば炭素数４～８（４、５、６、７、又は８）の不飽和炭化水素環が好ましく、ベンゼン環等が特に好ましい。また、本明細書において、飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合した構造を有する環としては、飽和炭化水素環及び／又は不飽和炭化水素環が２、３、又は４個縮合した環が好ましく、２又は３個縮合した環がより好ましい。より具体的には、例えば、デカヒドロナフタレン環、アダマンタン環、ナフタレン環、フェナントレン環、アントラセン環、ピレン環、トリフェニレン環、テトラリン環、１，２，３，４，５，６，７，８－オクタヒドロナフタレン環、ノルボルネン環等が挙げられる。 In the formula (1), the X ring represents a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed or connected. . In the present specification, as the saturated hydrocarbon ring, for example, a saturated hydrocarbon ring having 4 to 8 carbon atoms (4, 5, 6, 7, or 8) is preferable, and a cyclopentane ring, a cyclohexane ring and the like are particularly preferable. In the present specification, as the unsaturated hydrocarbon ring, for example, an unsaturated hydrocarbon ring having 4 to 8 carbon atoms (4, 5, 6, 7, or 8) is preferable, and a benzene ring or the like is particularly preferable. Further, in the present specification, as the ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed, the saturated hydrocarbon ring and / or unsaturated hydrocarbon ring is 2, 3, Alternatively, a ring having 4 condensed rings is preferable, and a ring having 2 or 3 condensed rings is more preferable. More specifically, for example, decahydronaphthalene ring, adamantane ring, naphthalene ring, phenanthrene ring, anthracene ring, pyrene ring, triphenylene ring, tetralin ring, 1,2,3,4,5,6,7,8- Examples include an octahydronaphthalene ring and a norbornene ring.
　なお、本明細書では、飽和炭化水素環又は不飽和炭化水素環、あるいは飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合した構造を有する環を、まとめて「炭化水素環」と呼ぶことがある。 In this specification, a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed is collectively referred to as a “hydrocarbon ring”. May be called.
　飽和炭化水素環及び／又は不飽和炭化水素環が２個連結した構造を有する環としては、式（２）： As a ring having a structure in which two saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are connected, the formula (2):
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
で表される環が好ましい。 The ring represented by is preferable.
　式（２）において、Ｘ１環及びＸ２環は、同一又は異なって、飽和炭化水素環又は不飽和炭化水素環を示す。すなわち、Ｘ１環及びＸ２環は、両方とも飽和炭化水素環であるか、両方とも不飽和炭化水素環であるか、一方が飽和炭化水素環でもう一方が不飽和炭化水素環である。Ｘ１環及びＸ２環が、両方とも飽和炭化水素環であるか、両方とも不飽和炭化水素環であることが好ましい。例えば、Ｘ１環及びＸ２環は、両方がベンゼン環、両方がシクロヘキサン環、又は一方がベンゼン環でもう一方がシクロヘキサン環、であることが好ましく、両方がベンゼン環であることがより好ましい。 In the formula (2), the X 1 ring and the X 2 ring are the same or different and represent a saturated hydrocarbon ring or an unsaturated hydrocarbon ring. That is, the X 1 ring and the X 2 ring are both saturated hydrocarbon rings, or both are unsaturated hydrocarbon rings, or one is a saturated hydrocarbon ring and the other is an unsaturated hydrocarbon ring. It is preferable that both the X 1 ring and the X 2 ring are saturated hydrocarbon rings or both are unsaturated hydrocarbon rings. For example, the X 1 ring and the X 2 ring are preferably both benzene rings, both cyclohexane rings, or one is a benzene ring and the other is a cyclohexane ring, and more preferably both are benzene rings.
　また、Ｙは、結合手、炭素数１～４のアルキル基で置換されていてもよい炭素数１～６のアルキレン基、酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、－ＳＯ－、又は－ＳＯ２－を示す。ここでの炭素数１～６のアルキレン基としては、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ヘキサメチレン基等が例示できる。また、置換基である炭素数１～４のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基等が例示できる。好ましい炭素数１～４のアルキル基で置換された炭素数１～６のアルキレン基としては、－ＣＨ（ＣＨ３）－、－Ｃ（ＣＨ３）２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２－、－ＣＨ２Ｃ（ＣＨ３）２ＣＨ２－等が例示できる。Ｙは好ましくは、結合手、酸素原子、メチレン基、ジメチルメチレン基、－Ｓ－、－ＳＯ２－であり、より好ましくは、結合手、ジメチルメチレン基、酸素原子、－ＳＯ２－である。 Y represents a bond, an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, an oxygen atom (—O—), a sulfur atom (—S—), —SO. -Or -SO 2 -is shown. Examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group. Examples of the alkyl group having 1 to 4 carbon atoms as a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Preferred examples of the alkylene group having 1 to 6 carbon atoms substituted by an alkyl group having 1 to 4 carbon atoms include —CH (CH 3 ) —, —C (CH 3 ) 2 —, —CH 2 CH (CH 3 ) CH. Examples thereof include 2- , -CH 2 C (CH 3 ) 2 CH 2- and the like. Y is preferably a bond, an oxygen atom, a methylene group, a dimethylmethylene group, —S—, —SO 2 —, and more preferably a bond, a dimethylmethylene group, an oxygen atom, —SO 2 —.
　式（２）で表わされる環はＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄで置換されている。式（１）中のＸ環が式（２）で表わされる環であって、ＲＸａ～ＲＸｄの３つが水素原子若しくはハロゲン原子又は低級炭素置換基で１つが式（３）の基である場合、Ｘ１環及びＸ２環のいずれが式（３）の基で置換されていてもよい。また、この場合、式（２）で表わされる環は０、１、２、又は３つのハロゲン原子又は低級炭素置換基で置換されるところ、ハロゲン原子又は低級炭素置換基の（Ｘ１環の置換数：Ｘ２環の置換数）は（１：０）、（０：１）、（２：０）、（１：１）、（０：２）、（３：０）、（２：１）、（１：２）、又は（０：３）であり得る。ＲＸａ～ＲＸｄの２つが水素原子若しくはハロゲン原子又は低級炭素置換基で２つが式（３）の基である場合、Ｘ１環及びＸ２環のいずれかが２つの式（３）の基で置換されていてもよく、Ｘ１環及びＸ２環が１つずつ式（３）の基で置換されていてもよく、Ｘ１環及びＸ２環が１つずつ式（３）の基で置換されていることが好ましい。また、この場合、式（２）で表わされる環は０、１、又は２つのハロゲン原子又は低級炭素置換基で置換されるところ、ハロゲン原子又は低級炭素置換基の（Ｘ１環の置換数：Ｘ２環の置換数）は（１：０）、（０：１）、（２：０）、（１：１）、又は（０：２）であり得る。ＲＸａ～ＲＸｄの１つが水素原子若しくはハロゲン原子又は低級炭素置換基で３つが式（３）の基である場合、Ｘ１環及びＸ２環のいずれかが３つの式（３）の基で置換されていてもよく、Ｘ１環が２つＸ２環が１つの式（３）の基で置換されていてもよく、Ｘ１環が１つＸ２環が２つの式（３）の基で置換されていてもよく、Ｘ１環が２つＸ２環が１つの式（３）の基で置換されている又はＸ１環が１つＸ２環が２つの式（３）の基で置換されていることが好ましい。また、この場合、式（２）で表わされる環は０又は１つのハロゲン原子又は低級炭素置換基で置換されるところ、ハロゲン原子又は低級炭素置換基の（Ｘ１環の置換数：Ｘ２環の置換数）は（１：０）、又は（０：１）であり得る。ＲＸａ～ＲＸｄの全てが式（３）の基である場合、Ｘ１環及びＸ２環のいずれかが４つの式（３）の基で置換されていてもよく、Ｘ１環が３つＸ２環が１つの式（３）の基で置換されていてもよく、Ｘ１環が１つＸ２環が３つの式（３）の基で置換されていてもよく、Ｘ１環が２つＸ２環が２つの式（３）の基で置換されていてもよく、Ｘ１環が２つＸ２環が２つの式（３）の基で置換されていることが好ましい。 The ring represented by formula (2) is substituted with R Xa , R Xb , R Xc , and R Xd . The ring X in the formula (1) is a ring represented by the formula (2), and three of R Xa to R Xd are a hydrogen atom, a halogen atom or a lower carbon substituent, and one is a group of the formula (3) In this case, either ring X 1 or ring X 2 may be substituted with a group of formula (3). In this case, when the ring represented by formula (2) is substituted with 0, 1, 2, or 3 halogen atoms or a lower-carbon substituent group, substituted (X 1 ring halogen atom or a lower carbon substituent Number: X 2 ring substitution number) is (1: 0), (0: 1), (2: 0), (1: 1), (0: 2), (3: 0), (2: 1) ), (1: 2), or (0: 3). When two of R Xa to R Xd are a hydrogen atom, a halogen atom or a lower carbon substituent and two are groups of the formula (3), either the X 1 ring or the X 2 ring is a group of the formula (3) in may be substituted, X 1 ring and X 2 rings may be substituted by one by one group of the formula (3), X 1 ring and X 2 ring group of the formula (3) one by one It is preferably substituted with. In this case, when the ring represented by formula (2) is substituted with 0, 1, or 2 halogen atom or a lower carbon substituent group, a halogen atom or a lower carbon substituent (X 1 substitution number rings: X 2 ring substitution number) can be (1: 0), (0: 1), (2: 0), (1: 1), or (0: 2). When one of R Xa to R Xd is a hydrogen atom, a halogen atom or a lower carbon substituent, and three are groups of the formula (3), either the X 1 ring or the X 2 ring is a group of the formula (3) May be substituted with two X 1 rings, one X 2 ring may be substituted with one group of formula (3), one X 1 ring and two X 2 rings with formula (3) In which two X 1 rings are substituted with one X 2 group or one X 1 ring and two X 2 rings are represented by formula (3). It is preferably substituted with a group of In this case, the ring represented by the formula (2) is substituted with 0 or 1 halogen atom or lower carbon substituent, and the halogen atom or lower carbon substituent (the number of substitution of X 1 ring: X 2 ring) The number of substitutions) may be (1: 0) or (0: 1). When all of R Xa to R Xd are groups of the formula (3), either the X 1 ring or the X 2 ring may be substituted with four groups of the formula (3), and the X 1 ring is 3 One X 2 ring may be substituted with one group of formula (3), one X 1 ring may be substituted with three X 2 rings with three groups of formula (3), and X 1 ring There may be substituted with two X 2 rings two formulas (3) group, it is preferred that X 1 ring are two X 2 ring is substituted by two groups of formula (3).
　式（１）の一部である基である、式（１’）： Formula (1 '), which is a group that is part of Formula (1):
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
（式（１’）中、Ｘ環は前記に同じ。）
で示される４価の基として、特に好ましくは以下の式で表される基が挙げられる。すなわち、 (In formula (1 ′), ring X is the same as above.)
As the tetravalent group represented by the formula, a group represented by the following formula is particularly preferable. That is,
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
又は Or
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
又は Or
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
（式（２ｇ）中、Ｙは前記に同じ。）
で表される基である。 (In formula (2 g ), Y is the same as above.)
It is group represented by these.
　式（３）において、Ｒ１は同一又は異なって、炭素数１～１８のアルキル基、炭素数２～９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基を示し、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子（好ましくは酸素原子）で置換されていてもよい。当該一部の炭素原子は、ケイ素原子に直接結合していない炭素原子であることが好ましい。また、当該置換されていてもよい一部の炭素原子は、１又は複数（例えば２、３、４、５、又は６）個の炭素原子であり、好ましくは１個の炭素原子である。なお、合成の簡便さの観点等から同一ケイ素原子に結合したＲ１は同一であることが好ましい。また、式（１）において存在する全てのＲ１が同一であることがより好ましい。 In the formula (3), R 1 is the same or different and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. Part of the carbon atoms may be substituted with at least one atom (preferably an oxygen atom) selected from the group consisting of an oxygen atom and a nitrogen atom. The partial carbon atoms are preferably carbon atoms that are not directly bonded to a silicon atom. The part of carbon atoms that may be substituted is 1 or plural (for example, 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom. Incidentally, R 1 bonded to the same silicon atom in view like the simplicity of the synthesis is preferably the same. Moreover, it is more preferable that all R 1 existing in the formula (1) is the same.
　Ｒ１で示される炭素数１～１８のアルキル基としては、直鎖又は分岐鎖状のアルキル基であり、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ネオペンチル基、ｔｅｒｔ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、２，２，４－トリメチルペンチル基、ｎ－オクチル基、イソオクチル基、ｎ－ノニル基、ｎ－デシル基、ｎ－ドデシル基等が挙げられる。好ましくは炭素数１～１０のアルキル基であり、より好ましくは炭素数１～６のアルキル基であり、さらに好ましくは炭素数１～３のアルキル基であり、特に好ましくはメチル基である。 The alkyl group having 1 to 18 carbon atoms represented by R 1 is a linear or branched alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl. Group, tert-butyl group, n-pentyl group, neopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, 2,2,4-trimethylpentyl group, n-octyl group, isooctyl group, n- Nonyl group, n-decyl group, n-dodecyl group and the like can be mentioned. An alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is further preferable, and a methyl group is particularly preferable.
　Ｒ１で示される炭素数２～９のアルケニル基としては、直鎖又は分岐鎖状のアルケニル基であり、例えば、ビニル基、アリル基、２－プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基等が挙げられる。好ましくは炭素数２～４のアルケニル基である。 The alkenyl group having 2 to 9 carbon atoms represented by R 1 is a linear or branched alkenyl group such as vinyl group, allyl group, 2-propenyl group, butenyl group, pentenyl group, hexenyl group, A heptenyl group, an octenyl group, a nonenyl group, etc. are mentioned. An alkenyl group having 2 to 4 carbon atoms is preferred.
　Ｒ１で示されるシクロアルキル基としては、３～８員環のシクロアルキル基が挙げられ、例えば、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、メチルシクロヘキシル基等が挙げられる。 Examples of the cycloalkyl group represented by R 1 include a 3- to 8-membered cycloalkyl group, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a methylcyclohexyl group.
　Ｒ１で示されるアリール基としては、単環又は二環のアリール基が挙げられ、例えば、フェニル基、トリル基、キシリル基、エチルフェニル基、ナフチル基等が挙げられる。中でも、フェニル基が好ましい。 Examples of the aryl group represented by R 1 include a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a naphthyl group. Of these, a phenyl group is preferred.
　Ｒ１で示されるアラルキル基としては、アリール基（特にフェニル基）で置換された炭素数１～４のアルキル基が挙げられ、例えば、ベンジル基、α－フェネチル基、β－フェネチル基、β－メチルフェネチル基等が挙げられる。 Examples of the aralkyl group represented by R 1 include an alkyl group having 1 to 4 carbon atoms substituted with an aryl group (especially a phenyl group). For example, benzyl group, α-phenethyl group, β-phenethyl group, β- Examples thereof include a methylphenethyl group.
　Ｒ１は、好ましくは炭素数１～３のアルキル基であり、より好ましくはメチル基である。 R 1 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
　式（３）において、Ｒ２は、炭素数１～１８のアルキレン基を示す。当該アルキレン基は、直鎖又は分岐鎖状のアルキレン基であり、好ましくは直鎖状のアルキレン基である。例えば、メチレン基、メチルメチレン基、エチルメチレン基、ジメチルメチレン基、ジエチルメチレン基、ジメチレン基（－ＣＨ２ＣＨ２－）、トリメチレン基（－ＣＨ２ＣＨ２ＣＨ２－）、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、ヘプタメチレン基、オクタメチレン基、ノナメチレン基、デカメチレン基、ウンデカメチレン基、ドデカメチレン基、トリデカメチレン基等が挙げられる。例えば、炭素数２～１８のアルキレン基、好ましくは炭素数２～１０のアルキレン基であり、より好ましくは炭素数２～８のアルキレン基であり、さらに好ましくは炭素数２～６のアルキレン基であり、特に好ましくは炭素数２～５のアルキレン基である。 In the formula (3), R 2 represents an alkylene group having 1 to 18 carbon atoms. The alkylene group is a linear or branched alkylene group, preferably a linear alkylene group. For example, methylene, methylmethylene, ethylmethylene, dimethylmethylene, diethylmethylene, dimethylene (—CH 2 CH 2 —), trimethylene (—CH 2 CH 2 CH 2 —), tetramethylene, penta Examples include a methylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, and a tridecamethylene group. For example, an alkylene group having 2 to 18 carbon atoms, preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, and further preferably an alkylene group having 2 to 6 carbon atoms. And particularly preferably an alkylene group having 2 to 5 carbon atoms.
　前記炭素数１～１８のアルキレン基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子（好ましくは酸素原子）で置換されていてもよい。当該一部の炭素原子は、ケイ素原子及び３～８員環又はエポキシ環のいずれにも直接結合していない炭素原子であることが好ましい。また、当該置換されていてもよい一部の炭素原子は、１又は複数（例えば２、３、４、５、又は６）個の炭素原子であり、好ましくは１個の炭素原子である。 In the alkylene group having 1 to 18 carbon atoms, some carbon atoms may be substituted with at least one atom (preferably an oxygen atom) selected from the group consisting of an oxygen atom and a nitrogen atom. The partial carbon atom is preferably a carbon atom that is not directly bonded to any of a silicon atom and a 3- to 8-membered ring or an epoxy ring. The part of carbon atoms that may be substituted is 1 or plural (for example, 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom.
　当該基としては、Ｒ２のケイ素原子に結合する側を（＊）とした場合に、例えば、（＊）－炭素数２～９のアルキレン－Ｏ－炭素数１～８のアルキレン－、好ましくは（＊）－炭素数２～４のアルキレン－Ｏ－炭素数１～３のアルキレン－、より好ましくは（＊）－炭素数２～４のアルキレン－Ｏ－炭素数１～２のアルキレン－、特に好ましくは（＊）－炭素数３のアルキレン－Ｏ－メチレン－が挙げられる。 Examples of the group include, when the side bonded to the silicon atom of R 2 is (*), for example, (*)-alkylene having 2 to 9 carbon atoms-O-alkylene having 1 to 8 carbon atoms, preferably (*)-C2-C4 alkylene-O-C1-C3 alkylene-, more preferably (*)-C2-C4 alkylene-O-C1-C2 alkylene-, especially Preferably, (*)-C3 alkylene-O-methylene- is used.
　具体的には、例えば、（＊）－（ＣＨ２）２－Ｏ－ＣＨ２－、（＊）－（ＣＨ２）３－Ｏ－ＣＨ２－、（＊）－（ＣＨ２）３－Ｏ－（ＣＨ２）２－、（＊）－（ＣＨ２）５－Ｏ－（ＣＨ２）４－などが挙げられ、これらの中でも（＊）－（ＣＨ２）３－Ｏ－ＣＨ２－が好ましい。 Specifically, for example, (*) — (CH 2 ) 2 —O—CH 2 —, (*) — (CH 2 ) 3 —O—CH 2 —, (*) — (CH 2 ) 3 —O -(CH 2 ) 2- , (*)-(CH 2 ) 5 -O- (CH 2 ) 4- and the like, among which (*)-(CH 2 ) 3 -O-CH 2- preferable.
　式（３）において、ｍは０～６の整数（すなわち０、１、２、３、４、５、又は６）を示す。また、ｎは０～３の整数（すなわち、０、１、２、又は３）を示す。ここで、式（３）のＲ２が結合している基（ケイ素原子に結合していない側）を式（４）で示す（以下、「式（４）の基」ということがある）と、以下のようになる。 In the formula (3), m represents an integer of 0 to 6 (that is, 0, 1, 2, 3, 4, 5, or 6). N represents an integer of 0 to 3 (that is, 0, 1, 2, or 3). Here, a group to which R 2 of formula (3) is bonded (side not bonded to a silicon atom) is represented by formula (4) (hereinafter, sometimes referred to as “group of formula (4)”). It becomes as follows.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
式（４）の基について、ｍが１～６の整数である場合を具体的に構造式で記載すると、
ｍ＝１の場合は For the group of formula (4), when m is an integer of 1 to 6, specifically described by the structural formula,
When m = 1
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
ｍ＝２の場合は When m = 2
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
ｍ＝３の場合は When m = 3
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
ｍ＝４の場合は When m = 4
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
ｍ＝５の場合は When m = 5
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
ｍ＝６の場合は When m = 6
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
と示される。 It is indicated.
　式（４）の基は、ｍが０の場合には、エポキシ環のみが残り、ｎが０～３の整数であるため、以下のいずれかの基を示す。 In the group of formula (4), when m is 0, only the epoxy ring remains and n is an integer of 0 to 3, and thus represents any of the following groups.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　式（３）において、Ｒ２及びＲ３は、３～８員環又はエポキシ環に結合する。なお、ｎは３～８員環又はエポキシ環に結合するＲ３の数を示している。 In the formula (3), R 2 and R 3 are bonded to a 3- to 8-membered ring or an epoxy ring. Note that n represents the number of R 3 bonded to a 3- to 8-membered ring or an epoxy ring.
　式（３）において、Ｒ３は同一又は異なって、炭素数１～１８のアルキル基、炭素数２～９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基を示し、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよい。当該一部の炭素原子は、３～８員環又はエポキシ環に直接結合していない炭素原子であることが好ましい。また、当該置換されていてもよい一部の炭素原子は、１又は複数（例えば２、３、４、５、又は６）個の炭素原子であり、好ましくは１個の炭素原子である。 In the formula (3), R 3 is the same or different and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. Part of the carbon atoms may be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. The partial carbon atom is preferably a carbon atom that is not directly bonded to a 3- to 8-membered ring or an epoxy ring. The part of carbon atoms that may be substituted is 1 or plural (for example, 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom.
　Ｒ３で示される炭素数１～１８のアルキル基、炭素数２～９のアルケニル基、シクロアルキル基、アリール基及びアラルキル基はそれぞれ、上記Ｒ１で示される対応する置換基と同様のものが挙げられる。 Alkyl group R 3 having 1 to 18 carbon atoms represented by an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, each aryl group and aralkyl group, those similar to the corresponding substituents represented by R 1 Can be mentioned.
　Ｒ３として、好ましくは炭素数１～３のアルキル基であり、より好ましくはメチル基又はエチル基である。 R 3 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.
　中でも好ましい式（３）の基の例として、Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは前記に同じであって、且つ、Ｒ１が全て同一であり、Ｒ３が（複数存在する場合には）全て同一である基が挙げられる。当該基は、式（１）で表されるエポキシ樹脂には１、２、３又は４存在し、それぞれの基が同一又は異なってよく、同一であることが好ましい。 Among these, as preferred examples of the group of the formula (3), R 1 , R 2 , R 3 , m, and n are the same as described above, and all of R 1 are the same, and R 3 is present (a plurality is present). In some cases) groups that are all identical are mentioned. The group is present in the epoxy resin represented by the formula (1) in 1, 2, 3 or 4, and each group may be the same or different, and is preferably the same.
　また式（４）の基として、特に好ましい具体例としては、Ｒ３は前記に同じであり、ｍが０、１、２、３又は４を示し、ｎが０、１又は２を示す基が挙げられ、なかでもより好ましくは、例えば以下の基（いずれもＲ３は前記に同じ）が挙げられる。 Further, as a particularly preferred specific example of the group of formula (4), R 3 is the same as above, and m is 0, 1, 2, 3 or 4, and n is 0, 1 or 2. Among them, more preferably, for example, the following groups (all of which R 3 is the same as described above) can be mentioned.
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　式（４）の基は、式（１）で表されるエポキシ樹脂には１，２、３又は４存在するが、それぞれの基が同一又は異なってよく、同一であることが好ましい。 The group of the formula (4) is 1, 2, 3 or 4 in the epoxy resin represented by the formula (1), but each group may be the same or different and is preferably the same.
　また、Ｘ環を構成する炭化水素環を構成する炭素原子であって且つＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄが結合していない炭素原子に結合した水素原子は、低級炭素置換基又はハロゲン原子（好ましくは低級炭素置換基）で置換されていてもよい。つまり、Ｘ環が飽和炭化水素環又は不飽和炭化水素環、あるいは飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合した構造を有する環である場合は、これらの環を構成する炭素原子であって且つＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄが結合していない炭素原子に結合した水素原子は、低級炭素置換基又はハロゲン原子（好ましくは低級炭素置換基）で置換されていてもよく、またＸ環が飽和炭化水素環及び／又は不飽和炭化水素環が２個連結した構造を有する環である場合は、これら連結された飽和炭化水素環及び／又は不飽和炭化水素環を構成する炭素原子であって且つＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄが結合していない炭素原子に結合した水素原子は、低級炭素置換基又はハロゲン原子（好ましくは低級炭素置換基）で置換されていてもよい。なお、Ｘ環が式（２）で表される環である場合をより具体的に説明すると、Ｘ１環及びＸ２環を構成する炭素原子であって且つＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄが結合していない炭素原子に結合した水素原子は、低級炭素置換基又はハロゲン原子（好ましくは低級炭素置換基）で置換されていてもよい、といえる。 In addition, a hydrogen atom bonded to a carbon atom constituting a hydrocarbon ring constituting the X ring and to which R Xa , R Xb , R Xc , and R Xd are not bonded is a lower carbon substituent or It may be substituted with a halogen atom (preferably a lower carbon substituent). That is, when the X ring is a saturated hydrocarbon ring or unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed, these rings are constituted. And a hydrogen atom bonded to a carbon atom to which R Xa , R Xb , R Xc , and R Xd are not bonded is substituted with a lower carbon substituent or a halogen atom (preferably a lower carbon substituent) And when the X ring is a ring having a structure in which two saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are connected, these connected saturated hydrocarbon rings and / or unsaturated hydrocarbon rings and R Xa a carbon atom constituting the hydrocarbon ring, R Xb, R Xc, and hydrogen atoms bonded to the carbon atom to which R Xd is not bound is a lower carbon substituent or a halogen atom (preferably lower carbon location It may be substituted by a group). The case where the X ring is a ring represented by the formula (2) will be described more specifically. The carbon atoms constituting the X 1 ring and the X 2 ring, and R Xa , R Xb , R Xc , And a hydrogen atom bonded to a carbon atom to which R Xd is not bonded may be substituted with a lower carbon substituent or a halogen atom (preferably a lower carbon substituent).
　本明細書においては、Ｘ環を構成する炭化水素環を構成する炭素原子であって且つＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄが結合していない炭素原子を「ＲＸａ－ｄ非結合炭素原子」ということがある。 In this specification, a carbon atom that constitutes a hydrocarbon ring constituting the X ring and to which R Xa , R Xb , R Xc , and R Xd are not bonded is referred to as “R Xa-d non-bonded”. Sometimes called a "carbon atom."
　ＲＸａ－ｄ非結合炭素原子に結合した水素原子が置換されていてもよい低級炭素置換基又はハロゲン原子は、１つのＲＸａ－ｄ非結合炭素原子に１つだけ結合することが好ましい。つまり、ＲＸａ－ｄ非結合炭素原子に結合した水素原子が置換される場合は、ＲＸａ－ｄ非結合炭素原子に結合した水素原子のうち１つの水素原子だけが低級炭素置換基又はハロゲン原子で置換されることが好ましい。また、当該置換の数（すなわち低級炭素置換基及びハロゲン原子の合計）は、ＲＸａ－ｄ非結合炭素原子の数より少ないことが好ましい。当該置換の数は、より具体的には１～６（１、２、３、４、５、又は６）が好ましく、１～４がより好ましく、１～２がさらに好ましい。また、特にＸ環が式（２）で表される環である場合には、置換される水素原子はＹが結合していない炭素原子に結合した水素原子であることが好ましい。 R Xa-d non-bonded hydrogen atoms bonded to carbon atoms may be substituted lower carbon substituent group or a halogen atom, it is preferable to only one single R Xa-d unbound carbon atoms bonds. That, R if Xa-d hydrogen atoms bonded to non-bonded carbon atoms is substituted, one hydrogen atom have a lower carbon substituent or a halogen atom of the hydrogen atoms bonded to R Xa-d unbound carbon atoms Is preferably substituted with. Further, the number of substitutions (that is, the total of the lower carbon substituent and the halogen atom) is preferably smaller than the number of R Xa-d non-bonded carbon atoms. More specifically, the number of the substitution is preferably 1 to 6 (1, 2, 3, 4, 5, or 6), more preferably 1 to 4, and still more preferably 1 to 2. In particular, when the X ring is a ring represented by the formula (2), the hydrogen atom to be substituted is preferably a hydrogen atom bonded to a carbon atom to which Y is not bonded.
　ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄのうち少なくとも１つが低級炭素置換基であって、且つＲＸａ－ｄ非結合炭素原子に低級炭素置換基が少なくとも１つ結合する場合、全ての低級炭素置換基が同一であることが好ましい。つまり、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄ中に低級炭素置換基が存在し、且つＲＸａ－ｄ非結合炭素原子に結合する低級炭素置換基が存在する場合、全ての低級炭素置換基が同一であることが好ましい。また、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄのうち少なくとも１つがハロゲン原子であって、且つＲＸａ－ｄ非結合炭素原子にハロゲン原子が少なくとも１つ結合する場合、全てのハロゲン原子が同一であることが好ましい。つまり、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄ中にハロゲン原子が存在し、且つＲＸａ－ｄ非結合炭素原子に結合するハロゲン原子が存在する場合、全てのハロゲン原子が同一であることが好ましい。 When at least one of R Xa , R Xb , R Xc , and R Xd is a lower carbon substituent and at least one lower carbon substituent is bonded to an R Xa-d unbonded carbon atom, It is preferred that the carbon substituents are the same. That is, if there is a lower carbon substituent in R Xa , R Xb , R Xc , and R Xd and there is a lower carbon substituent bonded to an R Xa-d unbonded carbon atom, all lower carbon substitutions It is preferred that the groups are the same. When at least one of R Xa , R Xb , R Xc , and R Xd is a halogen atom and at least one halogen atom is bonded to an R Xa-d non-bonded carbon atom, all the halogen atoms are It is preferable that they are the same. That is, when a halogen atom is present in R Xa , R Xb , R Xc , and R Xd and a halogen atom bonded to an R Xa-d unbonded carbon atom is present, all halogen atoms are the same. Is preferred.
　さらに具体的に説明すると、例えば、上記式（１’）で表される４価の基が More specifically, for example, a tetravalent group represented by the above formula (1 ') is
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
である場合、式（１）で表されるエポキシ樹脂として、式（１－Ｘ１） In the case where the epoxy resin represented by the formula (1) is represented by the formula (1-X1)
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
（式（１－Ｘ１）中、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、前記に同じであり、ＲＸｇ１及びＲＸｇ２は、同一又は異なって、水素原子、低級アルキル基、低級アルコキシ基、又は低級アルケニル基を示す。）で表されるエポキシ樹脂を好ましく例示できる。式（１－Ｘ１）において、ＲＸａ、ＲＸｂ、ＲＸｃ、ＲＸｄ、ＲＸｇ１及びＲＸｇ２が、それぞれ、ベンゼン環上の異なる炭素原子に結合していることがより好ましい。式（１－Ｘ１）で表されるエポキシ樹脂の中でも、ＲＸｇ１及びＲＸｇ２が水素原子であるものが好ましい。 (In the formula (1-X1), R Xa , R Xb , R Xc , and R Xd are the same as defined above, and R Xg1 and R Xg2 are the same or different and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group. An epoxy resin represented by a group or a lower alkenyl group is preferred. In the formula (1-X1), it is more preferable that R Xa , R Xb , R Xc , R Xd , R Xg1 and R Xg2 are bonded to different carbon atoms on the benzene ring, respectively. Among the epoxy resins represented by the formula (1-X1), those in which R Xg1 and R Xg2 are hydrogen atoms are preferable.
　式（１－Ｘ１）で表されるエポキシ樹脂の中でも、さらに好ましいものとして式（１－Ｘ１ａ）： Among the epoxy resins represented by the formula (1-X1), the more preferable one is the formula (1-X1a):
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
（式（１－Ｘ１ａ）中、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、前記に同じであり、ＲＸｇ１及びＲＸｇ２は、前記に同じ。）で表されるエポキシ樹脂や、式（１－Ｘ１ｂ）： (In the formula (1-X1a), R Xa , R Xb , R Xc , and R Xd are the same as described above, and R Xg1 and R Xg2 are the same as described above), (1-X1b):
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
（式（１－Ｘ１ｂ）中、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、前記に同じであり、ＲＸｇ１及びＲＸｇ２は、前記に同じ。）で表されるエポキシ樹脂が、例示できる。 (In formula (1-X1b), R Xa , R Xb , R Xc , and R Xd are the same as above, and R Xg1 and R Xg2 are the same as above). it can.
　式（１－Ｘ１ａ）で表されるエポキシ樹脂の中でも、例えば、ＲＸａ及びＲＸｂが水素原子でＲＸｃ及びＲＸｄが式（３）の基であり、ＲＸｇ１及びＲＸｇ２が水素原子である場合や、ＲＸａ及びＲＸｃが水素原子でＲＸｂ及びＲＸｄが式（３）の基であり、ＲＸｇ１及びＲＸｇ２が水素原子である場合がより好ましい。 Among the epoxy resins represented by the formula (1-X1a), for example, R Xa and R Xb are hydrogen atoms, R Xc and R Xd are groups of the formula (3), and R Xg1 and R Xg2 are hydrogen atoms. In some cases, R Xa and R Xc are hydrogen atoms, R Xb and R Xd are groups of the formula (3), and R Xg1 and R Xg2 are more preferably hydrogen atoms.
　また、式（１－Ｘ１ｂ）で表されるエポキシ樹脂の中でも、例えば、ＲＸａが水素原子でＲＸｂ、ＲＸｃ及びＲＸｄが式（３）の基であり、ＲＸｇ１及びＲＸｇ２が水素原子である場合がより好ましい。 Also, among the epoxy resins represented by the formula (1-X1b), for example, R Xa is a hydrogen atom, R Xb , R Xc and R Xd are groups of the formula (3), and R Xg1 and R Xg2 are hydrogen. More preferably, it is an atom.
　また、上記式（１’）で表される４価の基が In addition, the tetravalent group represented by the above formula (1 ')
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
（式（２ｇ）中、Ｙは前記に同じ。）
で表される基である場合、式（１）で表されるエポキシ樹脂として、式（１－Ｘ２） (In formula (2 g ), Y is the same as above.)
In the case of a group represented by formula (1), the epoxy resin represented by formula (1) is
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
（式（１－Ｘ２）中、Ｙは前記に同じであり、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、前記に同じであり、ＲＸ１１、ＲＸ１２、及びＲＸ１３並びにＲＸ２１、ＲＸ２２、及びＲＸ２３は、同一又は異なって、水素原子、低級アルキル基、低級アルコキシ基、又は低級アルケニル基を示す。）で表されるエポキシ樹脂も好ましく例示できる。式（１－Ｘ２）において、ＲＸａ、ＲＸｃ、ＲＸ１１、ＲＸ１２、及びＲＸ１３が、それぞれ異なる炭素原子に結合していることがより好ましく、また、ＲＸｂ、ＲＸｄ、ＲＸ２１、ＲＸ２２、及びＲＸ２３が、それぞれ異なる炭素原子に結合していることがより好ましい。また、ＲＸａ、ＲＸｂ、ＲＸｃ、ＲＸｄ、ＲＸ１１、ＲＸ１２、ＲＸ１３、ＲＸ２１、ＲＸ２２、及びＲＸ２３は、いずれもＹが結合した炭素原子には結合しない。 (In the formula (1-X2), Y is the same as defined above; R Xa , R Xb , R Xc , and R Xd are the same as defined above; R X11 , R X12 , R X13 , and R X21 , R X22 and R X23 may be the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group. In the formula (1-X2), R Xa , R Xc , R X11 , R X12 , and R X13 are more preferably bonded to different carbon atoms, and R Xb , R Xd , R X21 , More preferably, R X22 and R X23 are bonded to different carbon atoms. Also, R Xa , R Xb , R Xc , R Xd , R X11 , R X12 , R X13 , R X21 , R X22 , and R X23 are not bonded to the carbon atom to which Y is bonded.
　式（１－Ｘ２）で表されるエポキシ樹脂の中でも、さらに好ましいものとして式（１－Ｘ２ａ）： Among the epoxy resins represented by the formula (1-X2), the more preferable one is the formula (1-X2a):
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
（式（１－Ｘ２ａ）中、Ｙは前記に同じであり、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、前記に同じであり、ＲＸ１１、ＲＸ１２、及びＲＸ１３並びにＲＸ２１、ＲＸ２２、及びＲＸ２３は、同一又は異なって、水素原子、低級アルキル基、低級アルコキシ基、又は低級アルケニル基を示す。）で表されるエポキシ樹脂や、式（１－Ｘ２ｂ）： (In the formula (1-X2a), Y is the same as defined above; R Xa , R Xb , R Xc , and R Xd are the same as defined above; R X11 , R X12 , and R X13 and R X21 , R X22 and R X23 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group), or an epoxy resin represented by the formula (1-X2b):
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
（式（１－Ｘ２ｂ）中、Ｙは前記に同じであり、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、前記に同じであり、ＲＸ１１、ＲＸ１２、及びＲＸ１３並びにＲＸ２１、ＲＸ２２、及びＲＸ２３は、同一又は異なって、水素原子、低級アルキル基、低級アルコキシ基、又は低級アルケニル基を示す。）で表されるエポキシ樹脂や、式（１－Ｘ２ｃ）： (In the formula (1-X2b), Y is the same as defined above; R Xa , R Xb , R Xc , and R Xd are the same as defined above; R X11 , R X12 , R X13 , and R X21 , R X22 and R X23 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group), or an epoxy resin represented by the formula (1-X2c):
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
（式（１－Ｘ２ｃ）中、Ｙは前記に同じであり、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、前記に同じであり、ＲＸ１１、ＲＸ１２、及びＲＸ１３並びにＲＸ２１、ＲＸ２２、及びＲＸ２３は、同一又は異なって、水素原子、低級アルキル基、低級アルコキシ基、又は低級アルケニル基を示す。）で表されるエポキシ樹脂が、例示出来る。 (In the formula (1-X2c), Y is the same as defined above; R Xa , R Xb , R Xc , and R Xd are the same as defined above; R X11 , R X12 , and R X13 and R X21 , R X22 and R X23 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group.)
　式（１－Ｘ２ａ）で表されるエポキシ樹脂の中でも、例えば、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄが式（３）の基であり、ＲＸ１１及びＲＸ２１が低級炭素置換基であり、ＲＸ１２、ＲＸ１３、ＲＸ２２、及びＲＸ２３が水素原子である場合が好ましい。中でも、Ｙが炭素数１～４のアルキル基で置換されていてもよい炭素数１～６のアルキレン基（特に－Ｃ（ＣＨ３）２－）であり、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄが式（３）の基であり、ＲＸ１１及びＲＸ２１が低級アルコキシ基であり、ＲＸ１２、ＲＸ１３、ＲＸ２２、及びＲＸ２３が水素原子である場合が特に好ましい。これらの場合において、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄの式（３）の基が全て同一であり、ＲＸ１１及びＲＸ２１の低級炭素置換基が同一である場合が、より好ましい。 Among the epoxy resins represented by the formula (1-X2a), for example, R Xa , R Xb , R Xc , and R Xd are groups of the formula (3), and R X11 and R X21 are lower carbon substituents. Yes , it is preferable that R X12 , R X13 , R X22 , and R X23 are hydrogen atoms. Among them, Y is an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms (particularly —C (CH 3 ) 2 —), and R Xa , R Xb , R Xc , And R Xd is a group of the formula (3), R X11 and R X21 are lower alkoxy groups, and R X12 , R X13 , R X22 , and R X23 are particularly preferably hydrogen atoms. In these cases, it is more preferable that the groups of the formula (3) of R Xa , R Xb , R Xc and R Xd are all the same, and the lower carbon substituents of R X11 and R X21 are the same.
　また、式（１－Ｘ２ｂ）で表されるエポキシ樹脂の中でも、例えば、ＲＸａ及びＲＸｂが水素原子でＲＸｃ及びＲＸｄが式（３）の基であり、ＲＸ１１、ＲＸ１２、ＲＸ１３、ＲＸ２１、ＲＸ２２、及びＲＸ２３は水素原子の場合が好ましい。この場合において、ＲＸｃ及びＲＸｄの式（３）の基が同一である場合が、より好ましい。 Among the epoxy resins represented by the formula (1-X2b), for example, R Xa and R Xb are hydrogen atoms, R Xc and R Xd are groups of the formula (3), and R X11 , R X12 , R X13 , R X21 , R X22 , and R X23 are preferably a hydrogen atom. In this case, it is more preferable that the groups of the formula (3) of R Xc and R Xd are the same.
　また、式（１－Ｘ２ｃ）で表されるエポキシ樹脂の中でも、例えば、ＲＸａが水素原子でＲＸｂ、ＲＸｃ及びＲＸｄが式（３）の基であり、ＲＸ１１、ＲＸ１２、ＲＸ１３、ＲＸ２１、ＲＸ２２、及びＲＸ２３は水素原子の場合が好ましい。この場合において、ＲＸｂ、ＲＸｃ及びＲＸｄの式（３）の基が同一である場合が、より好ましい。 Further, among the epoxy resins represented by the formula (1-X2c), for example, R Xa is a hydrogen atom, R Xb , R Xc and R Xd are groups of the formula (3), and R X11 , R X12 , R X13 , R X21 , R X22 , and R X23 are preferably a hydrogen atom. In this case, it is more preferable that the groups of the formula (3) of R Xb , R Xc and R Xd are the same.
　本明細書において、式（１）におけるＸ環、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄ、並びに式（３）の基におけるＲ１、Ｒ２、Ｒ３、ｍ、及びｎに関する説明は、式（４）の基についての説明も含め、いずれも任意に組み合わせることができ、その組み合わせにより示されるいずれのエポキシ樹脂も本発明に用いることができる。 In the present specification, the explanation regarding the X ring, R Xa , R Xb , R Xc , and R Xd in formula (1), and R 1 , R 2 , R 3 , m, and n in the group of formula (3) In addition, any combination including the description of the group of the formula (4) can be arbitrarily combined, and any epoxy resin represented by the combination can be used in the present invention.
　式（１）において、（ｉｉａ）ＲＸａ－ｄ非結合炭素原子に結合した水素原子が置換されておらず、且つ、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄのうち、ＲＸａ及びＲＸｂが水素原子でＲＸｃ及びＲＸｄが式（３）の基であるか、（ｉｉｉａ）ＲＸａ－ｄ非結合炭素原子に結合した水素原子が置換されておらず、且つ、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄのうち、ＲＸａが水素原子でＲＸｂ、ＲＸｃ、及びＲＸｄが式（３）の基であるか、あるいは（ｉｖａ）ＲＸａ－ｄ非結合炭素原子に結合した水素原子が置換されておらず、且つ、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄの全てが式（３）の基であり得る。 In the formula (1), (iia) R Xa-d -bonded hydrogen atom has not been substituted in the non-bonded carbon atom, and, R Xa, R Xb, of R Xc, and R Xd, R Xa and R Xb is a hydrogen atom and R Xc and R Xd are groups of the formula (3), or (iii) the hydrogen atom bonded to the R Xa-d non-bonded carbon atom is not substituted, and R Xa , R Among Xb , R Xc , and R Xd , R Xa is a hydrogen atom and R Xb , R Xc , and R Xd are groups of the formula (3), or (iva) R Xa-d is bonded to a non-bonded carbon atom. The bonded hydrogen atoms are not substituted and all of R Xa , R Xb , R Xc , and R Xd can be groups of formula (3).
　（ｉｉａ）の場合、式（１）で示されるエポキシ樹脂は、次の式（１－ｉｉａ）： In the case of (ia), the epoxy resin represented by the formula (1) is represented by the following formula (1-ia):
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
〔式中、Ｘｉｉは、炭化水素環から２個の水素原子を除いて得られる２価の基、又は式（２ｇ－ｉｉａ）： [Wherein X ii represents a divalent group obtained by removing two hydrogen atoms from a hydrocarbon ring, or a formula (2 g -ia):
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
（式中、Ｙは、前記に同じ。）で表される２価の基を示し、
Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは前記に同じ。〕
で表されるエポキシ樹脂を好ましく包含する。なお、Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは、いずれも、それぞれ同一又は異なっていてよく、同一であることが好ましい。 (Wherein Y is the same as defined above),
R 1 , R 2 , R 3 , m, and n are the same as described above. ]
The epoxy resin represented by these is preferably included. Note that R 1 , R 2 , R 3 , m, and n may all be the same or different, and are preferably the same.
　Ｘｉｉで示される２価の基として、好ましくはシクロヘキサン－１，４－ジイル基、１，４－フェニレン基が挙げられ、より好ましくは１，４－フェニレン基である。 As divalent group represented by X ii, preferably cyclohexane-1,4-diyl group, a 1,4-phenylene group, more preferably a 1,4-phenylene group.
　式（２ｇ－ｉｉａ）で表される２価の基のうち好ましくは、式（２ｇ－ｉｉａ’）： Of the divalent groups represented by the formula (2 g -ia), the formula (2 g -ia ') is preferable:
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
（式中、Ｙは前記に同じ。）
で表される基である。 (Wherein Y is the same as above)
It is group represented by these.
　式（２ｇ－ｉｉａ’）において、Ｙが結合手、ジメチルメチレン基、酸素原子、又は－ＳＯ２－である基が特に好ましい。 In the formula (2 g -ia ′), a group in which Y is a bond, a dimethylmethylene group, an oxygen atom, or —SO 2 — is particularly preferable.
　Ｘｉｉとして、中でも好ましくはシクロヘキサン－１，４－ジイル基、１，４－フェニレン基、式（２ｇ－ｉｉａ’）が挙げられ、より好ましくは１，４－フェニレン基である。 As X ii, among them preferably a cyclohexane-1,4-diyl group, a 1,4-phenylene group, the formula (2 g -iia ') can be mentioned, more preferably a 1,4-phenylene group.
　例えば、式（１－ｉｉａ）において、ｍは同一で０、１、２、３、又は４（特に好ましくは、ｍは同一で０又は４）、ｎは同一で０（すなわち、Ｒ３により環は置換されていない）を、Ｘｉｉは炭化水素環（特に好ましくはベンゼン環）から２個の水素原子を除いて得られる２価の基を、Ｒ１は同一で炭素数１～３のアルキル基を、Ｒ２は同一でケイ素原子及び３～６員環又はエポキシ環のいずれにも直接結合していない１個の炭素原子が酸素原子で置換されていてもよい炭素数２～６のアルキレン基を、それぞれ示すことで表されるエポキシ樹脂を、より好ましく本発明に用いることができる。 For example, in the formula (1-ia), m is the same 0, 1, 2, 3, or 4 (particularly preferably, m is the same 0 or 4) and n is the same 0 (ie, R 3 is a ring X ii is a divalent group obtained by removing two hydrogen atoms from a hydrocarbon ring (particularly preferably a benzene ring), and R 1 is the same and has 1 to 3 carbon atoms. A group of 2 to 6 carbon atoms in which R 2 is the same and one carbon atom which is not directly bonded to any of a silicon atom and a 3- to 6-membered ring or an epoxy ring may be substituted with an oxygen atom An epoxy resin represented by showing each group can be more preferably used in the present invention.
　（ｉｉｉａ）の場合、式（１）で示されるエポキシ樹脂は、次の式（１－ｉｉｉａ）： In the case of (iii), the epoxy resin represented by the formula (1) is represented by the following formula (1-iii):
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
〔式中、Ｘｉｉｉは、炭化水素環から３個の水素原子を除いて得られる３価の基、又は式（２ｇ－ｉｉｉａ）： [Wherein X iii is a trivalent group obtained by removing three hydrogen atoms from a hydrocarbon ring, or a compound represented by the formula (2 g -iii):
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
（式中、Ｙは、前記に同じ。）で表される３価の基を示し、
Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは前記に同じ。〕
で表されるエポキシ樹脂を好ましく包含する。なお、Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは、いずれも、それぞれ同一又は異なっていてよく、同一であることが好ましい。 (Wherein Y represents the same as described above),
R 1 , R 2 , R 3 , m, and n are the same as described above. ]
The epoxy resin represented by these is preferably included. Note that R 1 , R 2 , R 3 , m, and n may all be the same or different, and are preferably the same.
　Ｘｉｉｉで示される３価の基として、好ましくは以下の基： The trivalent group represented by X iii is preferably the following group:
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
が挙げられる。 Is mentioned.
　式（２ｇ－ｉｉｉａ）で表される３価の基のうち好ましくは、式（２ｇ－ｉｉｉａ’）： Of the trivalent groups represented by the formula (2 g -iiia), the formula (2 g -iiiia ′):
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
（式中、Ｙは前記に同じ。）
で表される基である。 (Wherein Y is the same as above)
It is group represented by these.
　式（２ｇ－ｉｉｉａ’）において、Ｙが結合手、ジメチルメチレン基、酸素原子、又は－ＳＯ２－である基が特に好ましい。 In the formula (2 g -iii ′), a group in which Y is a bond, a dimethylmethylene group, an oxygen atom, or —SO 2 — is particularly preferable.
　例えば、式（１－ｉｉｉａ）において、ｍは同一で０、１、２、３、又は４（特に好ましくは、ｍは同一で０又は４）、ｎは同一で０（すなわち、Ｒ３により環は置換されていない）を、Ｘｉｉｉは炭化水素環（特に好ましくはベンゼン環）から３個の水素原子を除いて得られる３価の基を、Ｒ１は同一で炭素数１～３のアルキル基を、Ｒ２は同一でケイ素原子及び３～６員環又はエポキシ環のいずれにも直接結合していない１個の炭素原子が酸素原子で置換されていてもよい炭素数２～６のアルキレン基を、それぞれ示すことで表されるエポキシ樹脂を、より好ましく本発明に用いることができる。 For example, in the formula (1-iii), m is the same 0, 1, 2, 3, or 4 (particularly preferably, m is the same 0 or 4), and n is the same 0 (ie, R 3 represents a ring X iii is a trivalent group obtained by removing three hydrogen atoms from a hydrocarbon ring (particularly preferably a benzene ring), and R 1 is the same and has 1 to 3 carbon atoms. A group of 2 to 6 carbon atoms in which R 2 is the same and one carbon atom which is not directly bonded to any of a silicon atom and a 3- to 6-membered ring or an epoxy ring may be substituted with an oxygen atom An epoxy resin represented by showing each group can be more preferably used in the present invention.
　（ｉｖａ）の場合、式（１）で示されるエポキシ樹脂は、次の式（１－ｉｖａ）： In the case of (iva), the epoxy resin represented by formula (1) is represented by the following formula (1-iva):
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
〔式中、Ｘｉｖは、前記（１’）で示される４価の基であって、且つＸ環においてＲＸａ－ｄ非結合炭素原子に結合した水素原子が置換されていない基を示し、Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは前記に同じ。〕
で表されるエポキシ樹脂を包含する。なお、Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは、いずれも、それぞれ同一又は異なっていてよく、同一であることが好ましい。 [Wherein, X iv represents a tetravalent group represented by the above (1 ′) and a hydrogen atom bonded to an R Xa-d non-bonded carbon atom in the X ring is not substituted, R 1 , R 2 , R 3 , m, and n are the same as described above. ]
The epoxy resin represented by these is included. Note that R 1 , R 2 , R 3 , m, and n may all be the same or different, and are preferably the same.
　Ｘｉｖで示される４価の基として、好ましくは以下の基： The tetravalent group represented by X iv is preferably the following group:
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
が挙げられる。 Is mentioned.
　Ｘｉｖで示される４価の基として、式（２ｇ）で表される４価の基であってＲＸａ－ｄ非結合炭素原子に結合した水素原子が置換されていない基のうち、好ましくは、式（２ｇ－ｉｖａ’）： The tetravalent group represented by X iv is preferably a tetravalent group represented by the formula (2 g ), wherein a hydrogen atom bonded to an R Xa-d non-bonded carbon atom is not substituted. Is the formula (2 g -iva ′):
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
（式中、Ｙは前記に同じ。）
で表される基が挙げられる。 (Wherein Y is the same as above)
The group represented by these is mentioned.
　式（２ｇ－ｉｖａ’）において、Ｙが結合手、ジメチルメチレン基、酸素原子、又は－ＳＯ２－である基が特に好ましい。 In the formula (2 g -iva ′), a group in which Y is a bond, a dimethylmethylene group, an oxygen atom, or —SO 2 — is particularly preferable.
　例えば、式（１－ｉｖａ）において、ｍは同一で０、１、２、３、又は４（特に好ましくは、ｍは同一で０又は４）、ｎは同一で０（すなわち、Ｒ３により環は置換されていない）を、Ｘｉｖは炭化水素環（特に好ましくはベンゼン環）から４個の水素原子を除いて得られる４価の基を、Ｒ１は同一で炭素数１～３のアルキル基を、Ｒ２は同一でケイ素原子及び３～６員環又はエポキシ環のいずれにも直接結合していない１個の炭素原子が酸素原子で置換されていてもよい炭素数２～６のアルキレン基を、それぞれ示すことで表されるエポキシ樹脂を、より好ましく本発明に用いることができる。 For example, in the formula (1-iva), m is the same 0, 1, 2, 3, or 4 (particularly preferably, m is the same 0 or 4) and n is the same 0 (ie, R 3 is a ring X iv is a tetravalent group obtained by removing four hydrogen atoms from a hydrocarbon ring (particularly preferably a benzene ring), and R 1 is the same and has 1 to 3 carbon atoms. A group of 2 to 6 carbon atoms in which R 2 is the same and one carbon atom which is not directly bonded to any of a silicon atom and a 3- to 6-membered ring or an epoxy ring may be substituted with an oxygen atom An epoxy resin represented by showing each group can be more preferably used in the present invention.
　式（１）で表されるエポキシ樹脂のうち、さらに好ましいものとして、具体的には、例えば、式（１－ＩＩａ）： Of the epoxy resins represented by the formula (1), more preferable examples include, for example, the formula (1-IIa):
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
（式中、Ｒ１、Ｒ２、及びＸｉｉは前記に同じ。）
で表される化合物が挙げられる。 (In the formula, R 1 , R 2 and X ii are the same as above.)
The compound represented by these is mentioned.
　式（１－ＩＩａ）で表される化合物の中でも、Ｘｉｉが、１，４－フェニレン基又は式（２ｇ－ｉｉａ’）で表される基（好ましくは１，４－フェニレン基）であり、Ｒ１が同一又は異なって（好ましくは同一で）炭素数１～３のアルキル基（特にメチル基）であり、Ｒ２が同一又は異なって（好ましくは同一で）炭素数２～６のアルキレン基、（＊）－（ＣＨ２）２－Ｏ－ＣＨ２－、（＊）－（ＣＨ２）３－Ｏ－ＣＨ２－、（＊）－（ＣＨ２）３－Ｏ－（ＣＨ２）２－、又は（＊）－（ＣＨ２）５－Ｏ－（ＣＨ２）４－である化合物が好ましい。なお、上記同様、（＊）はＲ２のケイ素原子に結合する側を示す。
上記式（１－ＩＩａ）で表されるエポキシ樹脂のうち、さらに好ましいものとして、式（１－ＩＩａ１）： Among the compounds represented by the formula (1-IIa), X ii is a 1,4-phenylene group or a group represented by the formula (2 g- ia ′) (preferably a 1,4-phenylene group). R 1 is the same or different (preferably the same) and is an alkyl group having 1 to 3 carbon atoms (particularly a methyl group), and R 2 is the same or different (preferably the same) an alkylene having 2 to 6 carbon atoms Group (*) — (CH 2 ) 2 —O—CH 2 —, (*) — (CH 2 ) 3 —O—CH 2 —, (*) — (CH 2 ) 3 —O— (CH 2 ) A compound which is 2- or (*)-(CH 2 ) 5 -O- (CH 2 ) 4- is preferred. The above same, (*) indicates the side bonded to the silicon atoms of R 2.
Of the epoxy resins represented by the above formula (1-IIa), more preferred are those represented by the formula (1-IIa1):
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
（式中、Ｒ１及びＸｉｉは前記に同じ。）
又は式（１－ＩＩａ２）： (Wherein R 1 and X ii are the same as above).
Or formula (1-IIa2):
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000052
（式中、Ｒ１及びＸｉｉは前記に同じ。）
で表されるエポキシ樹脂が例示できる。なお、Ｒ１は同一又は異なっていてよく、同一であることが好ましい。 (Wherein R 1 and X ii are the same as above).
The epoxy resin represented by these can be illustrated. Note that R 1 may be the same or different, and is preferably the same.
　式（１－ＩＩａ１）又は（１－ＩＩａ２）において、Ｒ１は、同一又は異なって（好ましくは同一で）炭素数１～３のアルキル基（特にメチル基）であり、Ｘｉｉは、１，４－フェニレン基又は式（２ｇ－ｉｉａ’）で表される基であるものがより好ましい。 In the formula (1-IIa1) or (1-IIa2), R 1 is the same or different (preferably the same) and is an alkyl group having 1 to 3 carbon atoms (particularly a methyl group), and X ii is 1, More preferred is a 4-phenylene group or a group represented by the formula (2 g -ia ′).
　また、式（１）で表されるエポキシ樹脂のうち、より好ましいものとして、例えば、式（１－ＩＩｂ）： Further, among the epoxy resins represented by the formula (1), more preferable examples include, for example, the formula (1-IIb):
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053
（式中、Ｒ１、Ｒ２、Ｒ３、Ｘｉｉ、及びｎは前記に同じ。）
で表されるエポキシ樹脂を挙げることもできる。なお、Ｒ１、Ｒ２、Ｒ３、及びｎは、いずれも、それぞれ同一又は異なっていてよく、同一であることが好ましい。
式（１－ＩＩｂ）において、Ｘｉｉが１，４－フェニレン基又は式（２ｇ－ｉｉａ’）で表される基（好ましくは１，４－フェニレン基）であり、Ｒ１が同一又は異なって（好ましくは同一で）炭素数１～３のアルキル基（特にメチル基）であり、ｎが共に０（すなわち環はＲ３で置換されていない）であり、Ｒ２が同一又は異なって（好ましくは同一で）炭素数２～６のアルキレン基（好ましくはジメチレン基：－（ＣＨ２）２－）であるものがより好ましい。 (In the formula, R 1 , R 2 , R 3 , X ii , and n are the same as above.)
The epoxy resin represented by these can also be mentioned. Note that R 1 , R 2 , R 3 , and n may all be the same or different, and are preferably the same.
In the formula (1-IIb), X ii is a 1,4-phenylene group or a group represented by the formula (2 g -ia ′) (preferably a 1,4-phenylene group), and R 1 is the same or different. (Preferably the same) is an alkyl group having 1 to 3 carbon atoms (particularly a methyl group), n is both 0 (that is, the ring is not substituted with R 3 ), and R 2 is the same or different ( More preferably, it is the same and is an alkylene group having 2 to 6 carbon atoms (preferably a dimethylene group: — (CH 2 ) 2 —).
　また、式（１）で表されるエポキシ樹脂のうち、より好ましいものとして、さらに例えば、式（１－ＩＩＩａ）： Further, among the epoxy resins represented by the formula (1), more preferable examples include, for example, the formula (1-IIIa):
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
（式中、Ｒ１、Ｒ２、Ｒ３、Ｘｉｉｉ、及びｎは前記に同じ。）
で表されるエポキシ樹脂を挙げることもできる。なお、Ｒ１、Ｒ２、Ｒ３、及びｎは、いずれも、それぞれ同一又は異なっていてよく、同一であることが好ましい。
式（１－ＩＩＩａ）において、Ｘｉｉｉが (Wherein R 1 , R 2 , R 3 , X iii and n are the same as above)
The epoxy resin represented by these can also be mentioned. Note that R 1 , R 2 , R 3 , and n may all be the same or different, and are preferably the same.
In the formula (1-IIIa), X iii is
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
若しくは Or
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
又は式（２ｇ－ｉｉｉａ’）で表される基であり、Ｒ１が同一又は異なって（好ましくは同一で）炭素数１～３のアルキル基（特にメチル基）であり、ｎが共に０（すなわち環はＲ３で置換されていない）であり、Ｒ２が同一又は異なって（好ましくは同一で）炭素数２～６のアルキレン基（好ましくはジメチレン基：－（ＣＨ２）２－）であるものがより好ましい。 Or a group represented by the formula (2 g -iii ′), R 1 is the same or different (preferably the same) and is an alkyl group having 1 to 3 carbon atoms (particularly a methyl group), and both n are 0 (That is, the ring is not substituted with R 3 ), and R 2 is the same or different (preferably the same) and is an alkylene group having 2 to 6 carbon atoms (preferably a dimethylene group: — (CH 2 ) 2 —) Is more preferable.
　本発明のエポキシ樹脂組成物において、式（１）で表されるエポキシ樹脂は、単独で又は２種以上を組み合わせて用いることができる。 In the epoxy resin composition of the present invention, the epoxy resin represented by the formula (1) can be used alone or in combination of two or more.
　式（１）で表されるエポキシ樹脂は、公知の方法に基づいて又は準じて、例えば特許文献２（英国特許第１１２３９６０号公報）等の記載に基づいて又は準じて、製造することができる。また例えば、次の反応式で表される反応により式（１－ｉｉａ）で示されるエポキシ樹脂を製造することができる。 The epoxy resin represented by the formula (1) can be produced based on or according to a known method, for example, based on or according to the description of Patent Document 2 (UK Patent No. 1123960). Also, for example, an epoxy resin represented by the formula (1-ia) can be produced by a reaction represented by the following reaction formula.
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000057
（式中、Ｒ２Ａは、炭素数２～１８のアルケニル基であり、この基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよい。Ｒ１、Ｒ２、Ｒ３、及びＸｉｉは前記に同じ。） (In the formula, R 2A is an alkenyl group having 2 to 18 carbon atoms, and in this group, some carbon atoms are substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. R 1 , R 2 , R 3 , and X ii are the same as above.)
　Ｒ２Ａで示される炭素数２～１８のアルケニル基としては、直鎖又は分岐鎖状のアルケニル基であり、直鎖状が好ましい。具体的には、例えば、ビニル基、アリル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノルボルネニル基、シクロヘキセニル基等が挙げられる。好ましくは炭素数２～１０のアルケニル基であり、より好ましくは炭素数２～８のアルケニル基であり、さらに好ましくは炭素数２～６のアルケニル基であり、特に好ましくはビニル基、アリル基又はブテニル基である。なお、当該アルケニル基は、α－アルケニル基であることが好ましい。 The alkenyl group having 2 to 18 carbon atoms represented by R 2A is a linear or branched alkenyl group, and is preferably a straight chain. Specific examples include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a norbornenyl group, and a cyclohexenyl group. An alkenyl group having 2 to 10 carbon atoms is preferred, an alkenyl group having 2 to 8 carbon atoms is more preferred, an alkenyl group having 2 to 6 carbon atoms is more preferred, and a vinyl group, allyl group or It is a butenyl group. The alkenyl group is preferably an α-alkenyl group.
　これらの炭素数２～１８のアルケニル基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子（好ましくは酸素原子）で置換されていてもよい。当該一部の炭素原子は、エポキシ環に直接結合していない炭素原子であることが好ましい。また、当該置換されてもよい一部の炭素原子は、１又は複数（例えば２、３、４、５、又は６）個の炭素原子であり、好ましくは１個の炭素原子である。当該基としては、例えば、炭素数２～９アルケニル－Ｏ－炭素数１～８アルキレン－、好ましくは炭素数２～４アルケニル－Ｏ－炭素数１～３アルキレン－、より好ましくは炭素数２～４アルケニル－Ｏ－炭素数１～２アルキレン－、特に好ましくは炭素数３アルケニル－Ｏ－ＣＨ２－が挙げられる。具体的には、例えば、ＣＨ２＝ＣＨ－Ｏ－ＣＨ２－、ＣＨ２＝ＣＨ－ＣＨ２－Ｏ－ＣＨ２－、ＣＨ２＝ＣＨ－ＣＨ２－Ｏ－（ＣＨ２）２－、ＣＨ２＝ＣＨ－（ＣＨ２）３－Ｏ－（ＣＨ２）４－などが挙げられ、これらの中でもＣＨ２＝ＣＨ－ＣＨ２－Ｏ－ＣＨ２－（アリルオキシメチル基）が好ましい。 In these alkenyl groups having 2 to 18 carbon atoms, some carbon atoms may be substituted with at least one atom (preferably an oxygen atom) selected from the group consisting of an oxygen atom and a nitrogen atom. The some carbon atoms are preferably carbon atoms not directly bonded to the epoxy ring. The part of carbon atoms that may be substituted is 1 or a plurality of (for example, 2, 3, 4, 5, or 6) carbon atoms, and preferably one carbon atom. Examples of the group include 2 to 9 alkenyl-O-carbon having 1 to 8 carbon atoms, preferably 2 to 4 alkenyl-O carbon atoms having 1 to 3 carbon atoms, more preferably 2 to 3 carbon atoms. Examples thereof include 4 alkenyl-O-alkylene having 1 to 2 carbon atoms, particularly preferably 3 alkenyl-O—CH 2 —. Specifically, for example, CH 2 ═CH—O—CH 2 —, CH 2 ═CH—CH 2 —O—CH 2 —, CH 2 ═CH—CH 2 —O— (CH 2 ) 2 —, CH 2 = CH- (CH 2) 3 -O- (CH 2) 4 - is like, among these CH 2 = CH-CH 2 -O -CH 2 - ( allyloxymethyl group).
　式（１－ｉｉａ）で表されるエポキシ樹脂は、式（５－ｉｉａ）で表される化合物と式（６）で表される化合物をヒドロシリル化反応させて製造することができる。ヒドロシリル化反応は、通常、触媒の存在下、溶媒の存在下又は非存在下で実施することができる。また、式（５－ｉｉａ）で表される化合物にかえて、式（５－ｉｉｉａ）： The epoxy resin represented by the formula (1-ia) can be produced by subjecting the compound represented by the formula (5-ia) and the compound represented by the formula (6) to a hydrosilylation reaction. The hydrosilylation reaction can usually be carried out in the presence of a catalyst, in the presence or absence of a solvent. Further, in place of the compound represented by the formula (5-ia), the formula (5-iii):
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000058
（式中、Ｒ１及びＸｉｉｉは前記に同じ。）
　又は式（５－ｉｖａ）： (Wherein R 1 and X iii are the same as above)
Or the formula (5-iva):
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
（式中、Ｒ１及びＸｉｉｉは前記に同じ。）
又は式（５－ｉａ）： (Wherein R 1 and X iii are the same as above)
Or formula (5-ia):
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
（式中、Ｘｉは炭化水素環から１個の水素原子を除いて得られる１価の基を示し、Ｒ１は前記に同じ。）
で表される化合物を用いることにより、上記式（１－ｉｉｉａ）又は（１－ｉｖａ）で表されるエポキシ樹脂や１個の式（３）の基が炭化水素環に結合した構造を有するエポキシ樹脂を製造することもできる。また、これらの化合物の構造において、Ｘｉ～Ｘｉｖが、それぞれ、Ｘ環から１個の水素原子を除いて得られる１価の基、Ｘ環から２個の水素原子を除いて得られる２価の基、Ｘ環から３個の水素原子を除いて得られる３価の基、又はＸ環から４個の水素原子を除いて得られる４価の基、に置換された構造の化合物を用いることで、式（１）で示される種々の化合物を製造することができる。 (In the formula, X i represents a monovalent group obtained by removing one hydrogen atom from a hydrocarbon ring, and R 1 is the same as above.)
An epoxy resin represented by the above formula (1-iii) or (1-iva) or an epoxy having a structure in which one group of the formula (3) is bonded to a hydrocarbon ring. Resins can also be produced. In the structures of these compounds, X i to X iv are each a monovalent group obtained by removing one hydrogen atom from the X ring, and 2 obtained by removing two hydrogen atoms from the X ring. Use a compound having a structure substituted with a valent group, a trivalent group obtained by removing three hydrogen atoms from the X ring, or a tetravalent group obtained by removing four hydrogen atoms from the X ring Thus, various compounds represented by the formula (1) can be produced.
　ヒドロシリル化反応に用いられる触媒は、公知の触媒でよく、例えば、白金カーボン、塩化白金酸、白金のオレフィン錯体、白金のアルケニルシロキサン錯体、白金のカルボニル錯体等の白金系触媒；トリス（トリフェニルフォスフィン）ロジウム等のロジウム系触媒；ビス(シクロオクタジエニル)ジクロロイリジウム等のイリジウム系触媒が挙げられる。上記の触媒は溶媒和物（例えば、水和物、アルコール和物等）の形態であってもよく、また使用にあたり触媒をアルコール（例えば、エタノール等）に溶解して溶液の形態で用いることもできる。なお触媒は、単独で又は２種以上を組み合わせて用いることができる。 The catalyst used in the hydrosilylation reaction may be a known catalyst such as platinum catalyst such as platinum carbon, chloroplatinic acid, platinum olefin complex, platinum alkenylsiloxane complex, platinum carbonyl complex, etc .; Fin) rhodium and other rhodium catalysts; and iridium catalysts such as bis (cyclooctadienyl) dichloroiridium. The above catalyst may be in the form of a solvate (for example, hydrate, alcohol solvate, etc.). In use, the catalyst may be dissolved in an alcohol (for example, ethanol) and used in the form of a solution. it can. In addition, a catalyst can be used individually or in combination of 2 or more types.
　触媒の使用量は、触媒としての有効量でよく、例えば、上記式（５－ｉａ）、（５－ｉｉａ）、（５－ｉｉｉａ）、又は（５－ｉｖａ）で表される化合物と式（６）で表される化合物との合計量１００質量部に対して ０．００００１～２０質量部、好ましくは０．０００５～５質量部である。 The amount of the catalyst used may be an effective amount as a catalyst. For example, the compound represented by the above formula (5-ia), (5-ia), (5-iiia), or (5-iva) and the formula ( The amount is 0.00001 to 20 parts by weight, preferably 0.0005 to 5 parts by weight, based on 100 parts by weight in total with the compound represented by 6).
　前記ヒドロシリル化反応は溶媒を用いなくても進行するが、溶媒を用いることにより穏和な条件で反応を行うことができる。溶媒としては、例えば、トルエン、キシレンなどの芳香族炭化水素溶媒；ヘキサン、オクタンなどの脂肪族炭化水素溶媒；テトラヒドロフラン、ジオキサンなどのエーテル系溶媒；エタノール、イソプロパノールなどのアルコール系溶媒などが挙げられ、これらは単独で又は２種以上組み合わせてもよい。 The hydrosilylation reaction proceeds without using a solvent, but the reaction can be performed under mild conditions by using a solvent. Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane and octane; ether solvents such as tetrahydrofuran and dioxane; alcohol solvents such as ethanol and isopropanol; These may be used alone or in combination of two or more.
　式（６）で表される化合物の使用量は、例えば、式（５－ｉａ）、（５－ｉｉａ）、（５－ｉｉｉａ）、又は（５－ｉｖａ）で表される化合物中のＳｉ－Ｈ基１モルに対して、通常、０．５～２モル、好ましくは０．６～１．５モル、より好ましくは０．８～１．２モルである。 The amount of the compound represented by the formula (6) is, for example, Si— in the compound represented by the formula (5-ia), (5-ia), (5-iii), or (5-iva). The amount is usually 0.5 to 2 mol, preferably 0.6 to 1.5 mol, more preferably 0.8 to 1.2 mol, relative to 1 mol of the H group.
　反応温度は、通常０℃～１５０℃、好ましくは１０℃～１２０℃であり、反応時間は、通常１時間～２４時間程度である。 The reaction temperature is usually 0 ° C. to 150 ° C., preferably 10 ° C. to 120 ° C., and the reaction time is usually about 1 hour to 24 hours.
　反応終了後、反応液から溶媒を留去するなど、公知の単離手法を用いることにより、式（１）で表されるエポキシ樹脂を得ることができる。 After completion of the reaction, the epoxy resin represented by the formula (1) can be obtained by using a known isolation method such as distilling off the solvent from the reaction solution.
　本発明に用いられる活性エステル化合物は、エステル基（好ましくは反応活性の高いエステル基）を有する化合物である。活性エステル化合物としては、具体的には、エステル基を１分子中に２個以上有する化合物が好適である。このような化合物として、例えば、フェノールエステル類、チオフェノールエステル類、Ｎ－ヒドロキシアミンエステル類、複素環ヒドロキシ化合物のエステル類等のエステル基を１分子中に２個以上有する化合物が好ましい。 The active ester compound used in the present invention is a compound having an ester group (preferably an ester group having high reaction activity). As the active ester compound, specifically, a compound having two or more ester groups in one molecule is preferable. As such compounds, for example, compounds having two or more ester groups in one molecule such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds are preferable.
　また、活性エステル化合物は、カルボン酸化合物及び／又はチオカルボン酸化合物とヒドロキシ化合物及び／又はチオール化合物との縮合反応によって得られる化合物（すなわち、カルボン酸化合物及びチオカルボン酸化合物からなる群より選択される少なくとも１種と、ヒドロキシ化合物及びチオール化合物からなる群より選択される少なくとも１種との、縮合物）が好ましい。特に耐熱性向上の観点から、カルボン酸化合物とヒドロキシ化合物とから得られる縮合物が好ましく、カルボン酸化合物とフェノール化合物及び／又はナフトール化合物とから得られる縮合物がより好ましい。このような縮合物（活性エステル化合物）は、エポキシ樹脂硬化剤として好ましく用いることができる。 The active ester compound is a compound obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound (that is, at least selected from the group consisting of a carboxylic acid compound and a thiocarboxylic acid compound). 1 type and the condensate of at least 1 sort (s) selected from the group which consists of a hydroxy compound and a thiol compound) are preferable. In particular, from the viewpoint of improving heat resistance, a condensate obtained from a carboxylic acid compound and a hydroxy compound is preferred, and a condensate obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Such a condensate (active ester compound) can be preferably used as an epoxy resin curing agent.
　カルボン酸化合物としては、例えば安息香酸、酢酸、コハク酸、マレイン酸、イタコン酸、フタル酸、イソフタル酸、テレフタル酸、ピロメリット酸等が挙げられる。 Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
　チオカルボン酸化合物としては、例えば、チオ酢酸、チオ安息香酸等が挙げられる。 Examples of the thiocarboxylic acid compound include thioacetic acid and thiobenzoic acid.
　ヒドロキシ化合物としては、例えば、フェノール化合物又はナフトール化合物が挙げられ、具体的には、例えばハイドロキノン、レゾルシン、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、フェノールフタリン、メチル化ビスフェノールＡ、メチル化ビスフェノールＦ、メチル化ビスフェノールＳ、フェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール、カテコール、α－ナフトール、β－ナフトール、１，５－ジヒドロキシナフタレン、１，６－ジヒドロキシナフタレン、２，６－ジヒドロキシナフタレン、ジヒドロキシベンゾフェノン、トリヒドロキシベンゾフェノン、テトラヒドロキシベンゾフェノン、フロログルシン、ベンゼントリオール、ジシクロペンタジエニルジフェノール、フェノールノボラック等が挙げられる。 Examples of the hydroxy compound include a phenol compound or a naphthol compound. Specifically, for example, hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methyl Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxy Benzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, phenol novolac, etc. Can be mentioned.
チオール化合物としては、例えば、ベンゼンジチオール、トリアジンジチオール等が挙げられる。 Examples of the thiol compound include benzenedithiol and triazinedithiol.
　活性エステル化合物として、例えば特開２００９－２３５１６５号公報、特開２００４－２７７４６０号公報、又はＷＯ２０１３／０６１６８８に開示されている活性エステル化合物を用いることもできる。特開２００９－２３５１６５号公報に記載の活性エステル化合物を用いることがより好ましい。特開２００９－２３５１６５号公報、特開２００４－２７７４６０号公報、及びＷＯ２０１３／０６１６８８の明細書および／または図面に記載される内容は参照により本明細書に組み込まれる。 As the active ester compound, for example, active ester compounds disclosed in JP2009-235165A, JP2004-277460A, or WO2013 / 061688 can be used. It is more preferable to use an active ester compound described in JP-A-2009-235165. The contents described in the specifications and / or drawings of JP 2009-235165 A, JP 2004-277460 A, and WO 2013/061688 are incorporated herein by reference.
　活性エステル化合物としては、中でもジシクロペンタジエニルジフェノール構造を含むエステル化合物が好ましい。 As the active ester compound, an ester compound containing a dicyclopentadienyl diphenol structure is particularly preferable.
　活性エステル化合物として、式（７）：  As an active ester compound, formula (7):
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000061
　（式中、Ｒ４はフェニル基又はナフチル基であり、ｙは０又は１の整数を表し、ｚは繰り返し単位の平均で０．０５～２．５である。）で表される化合物が特に好ましい。Ｒ４は好ましくはナフチル基である。ｙは好ましくは０である。ｚは好ましくは０．２５～１．５である。電気特性・耐熱性の観点からＲ４がナフチル基であり、ｙが０であり、ｚが０．２５～１．５であることがより好ましい。 (Wherein R 4 represents a phenyl group or a naphthyl group, y represents an integer of 0 or 1, and z represents an average of repeating units of 0.05 to 2.5). preferable. R 4 is preferably a naphthyl group. y is preferably 0. z is preferably 0.25 to 1.5. From the viewpoint of electrical characteristics and heat resistance, it is more preferable that R 4 is a naphthyl group, y is 0, and z is 0.25 to 1.5.
　また、活性エステル化合物として、分子鎖末端にアリールオキシカルボニル基を有する、芳香族多価カルボン酸残基と芳香族多価ヒドロキシ化合物残基とからなるポリエステルであって、当該芳香族多価ヒドロキシ化合物残基が式（８ａ）： Further, as an active ester compound, a polyester comprising an aromatic polyvalent carboxylic acid residue and an aromatic polyvalent hydroxy compound residue having an aryloxycarbonyl group at a molecular chain end, the aromatic polyvalent hydroxy compound The residue is of formula (8a):
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000062
（式中、ｋは０又は１を示す。）で表される基であり、当該芳香族多価カルボン酸残基が式（８ｂ）： (Wherein k represents 0 or 1), and the aromatic polyvalent carboxylic acid residue is represented by formula (8b):
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000063
（式中、Ａは、同一又は異なって、炭素数１、２、３又は４のアルキル基、炭素数１、２、３又は４のアルコキシ基、又はハロゲン原子を示し、ａは０、１、２、３、又は４を示す。）で表される基であり、当該アリールオキシカルボニル基が式（８ｃ－１）： (In the formula, A is the same or different and represents an alkyl group having 1, 2, 3 or 4 carbon atoms, an alkoxy group having 1, 2, 3 or 4 carbon atoms, or a halogen atom, and a is 0, 1, 2, 3 or 4), and the aryloxycarbonyl group is represented by the formula (8c-1):
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000064
（式中、Ｐは、同一又は異なって、炭素数１、２、３又は４のアルキル基、炭素数１、２、３又は４のアルコキシ基、ニトロ基、又はハロゲン原子を示し、ｐは０、１、２、３、４、又は５を示す。）で表される基であるか、又は式（８ｃ－２）： (Wherein P is the same or different and represents an alkyl group having 1, 2, 3 or 4 carbon atoms, an alkoxy group having 1, 2, 3 or 4 carbon atoms, a nitro group, or a halogen atom, and p is 0. , 1, 2, 3, 4 or 5), or a group represented by formula (8c-2):
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000065
（式中、Ｕ及びＴは、同一又は異なって、炭素数１、２、３又は４のアルキル基、炭素数１、２、３又は４のアルコキシ基、ニトロ基、又はハロゲン原子を示し、ｕは０、１、２、又は３を示し、ｔは０、１、２、３、又は４を示す。）で表される基であるか、又は式（８ｃ－３）： (In the formula, U and T are the same or different and each represents an alkyl group having 1, 2, 3 or 4 carbon atoms, an alkoxy group having 1, 2, 3 or 4 carbon atoms, a nitro group, or a halogen atom; Represents 0, 1, 2, or 3, and t represents 0, 1, 2, 3, or 4.), or a group represented by formula (8c-3):
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000066

（式中、Ｑ及びＲは、同一又は異なって、炭素数１、２、３又は４のアルキル基、炭素数１、２、３又は４のアルコキシ基、ニトロ基、又はハロゲン原子を示し、ｑは０、１、２、３、又は４を示し、ｒは０、１、２、３、４、又は５を示す。Ｚは単結合、－Ｏ－、－ＣＯ－、－ＣＨ２－、－Ｃ（ＣＨ３）２－、または－ＳＯ２－を示す。）で表される基である、ポリエステルも好ましく挙げられる。
Wherein Q and R are the same or different and each represents an alkyl group having 1, 2, 3 or 4 carbon atoms, an alkoxy group having 1, 2, 3 or 4 carbon atoms, a nitro group, or a halogen atom; Represents 0, 1, 2, 3, or 4, and r represents 0, 1, 2, 3, 4, or 5. Z represents a single bond, —O—, —CO—, —CH 2 —, — A polyester represented by C (CH 3 ) 2 — or —SO 2 — is also preferred.
　ここでの炭素数１、２、３又は４のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基が挙げられ、炭素数１、２、３又は４のアルコキシ基としては、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基、イソブトキシ基、ｔ－ブトキシ基が挙げられる。 Examples of the alkyl group having 1, 2, 3 or 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. Examples of 1, 2, 3 or 4 alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and t-butoxy.
　このようなポリエステルとして、特に好ましいものとして、下記表１に記載する、芳香族多価カルボン酸の酸ハロゲン化物の少なくとも１種、芳香族モノヒドロキシ化合物の少なくとも１種、及び芳香族多価ヒドロキシ化合物（ジシクロペンタジエニルジフェノール）、とを反応させて得られるポリエステルが例示される。 Particularly preferable examples of such polyesters include at least one kind of an acid halide of an aromatic polyvalent carboxylic acid, at least one kind of an aromatic monohydroxy compound, and an aromatic polyvalent hydroxy compound described in Table 1 below. Examples thereof include polyesters obtained by reacting (dicyclopentadienyl diphenol).
Figure JPOXMLDOC01-appb-T000067
Figure JPOXMLDOC01-appb-T000067
　活性エステル化合物は単独で又は２種以上を組み合わせて用いることが出来る。 The active ester compounds can be used alone or in combination of two or more.
　また市販のエステル化合物を本発明に活性エステル化合物として用いることもできる。このような市販のエステル化合物としては、ジシクロペンタジエニルジフェノール構造を含むエステル化合物、フェノールノボラックのアセチル化物、フェノールノボラックのベンゾイル化物等が好ましく、なかでもジシクロペンタジエニルジフェノール構造を含むエステル化合物がより好ましい。 Commercially available ester compounds can also be used as the active ester compound in the present invention. As such a commercially available ester compound, an ester compound containing a dicyclopentadienyl diphenol structure, an acetylated product of a phenol novolak, a benzoylated product of a phenol novolak, etc. are preferable, and among them, a dicyclopentadienyl diphenol structure is included. An ester compound is more preferable.
　より詳細には、例えば、ジシクロペンタジエニルジフェノール構造を含むエステル化合物として、ＥＸＢ９４５１、ＥＸＢ９４６０、ＥＸＢ９４６０Ｓ－６５Ｔ、ＨＰＣ－８０００－６５Ｔ（ＤＩＣ社製、活性基当量約２２３）、フェノールノボラックのアセチル化物としてＤＣ８０８（三菱化学社製、活性基当量約１４９）、フェノールノボラックのベンゾイル化物としてＹＬＨ１０２６（三菱化学社製、活性基当量約２００）、ＹＬＨ１０３０（三菱化学社製、活性基当量約２０１）、ＹＬＨ１０４８（三菱化学社製、活性基当量約２４５）、等が挙げられる。 More specifically, for example, as ester compounds containing a dicyclopentadienyl diphenol structure, EXB9451, EXB9460, EXB9460S-65T, HPC-8000-65T (manufactured by DIC, active group equivalent of about 223), phenol novolac acetyl DC808 (Mitsubishi Chemical Corporation, active group equivalent of about 149) as a compound, YLH1026 (Mitsubishi Chemical Corporation, active group equivalent of about 200), YLH1030 (Mitsubishi Chemical Corporation, active group equivalent of about 201) as a benzoylated phenol novolak, YLH1048 (manufactured by Mitsubishi Chemical Corporation, active group equivalent of about 245), and the like.
　上記式（７）で表される市販の活性エステル化合物としては、ＨＰＣ－８０００－６５Ｔ（ＤＩＣ社製、エステル当量 約２２３ｇ／ｅｑ）等が挙げられる。なお、ＨＰＣ－８０００－６５Ｔは、次に示す反応によりエポキシ樹脂を硬化させることが知られている（次の式において、ＨＰＣ－８０００－６５ＴはＲ’’－ＣＯ－Ｏ－Ｒ’’’で表わされる）。
Figure JPOXMLDOC01-appb-C000068
 Examples of commercially available active ester compounds represented by the above formula (7) include HPC-8000-65T (manufactured by DIC, ester equivalent of about 223 g / eq). HPC-8000-65T is known to cure an epoxy resin by the following reaction (in the following formula, HPC-8000-65T is R ″ —CO—O—R ′ ″). Represented).
Figure JPOXMLDOC01-appb-C000068
　本発明に係るエポキシ樹脂組成物における活性エステル化合物の配合割合は、本発明の効果を発揮できる範囲であれば特に制限されない。 The blending ratio of the active ester compound in the epoxy resin composition according to the present invention is not particularly limited as long as the effect of the present invention can be exhibited.
　エポキシ樹脂と活性エステル化合物の配合割合としては、例えば、エポキシ樹脂のエポキシ基と活性エステル化合物のエステル基の当量比（エポキシ基／エステル基）が０．２～３となる割合であることが好ましく、０．５～１．５であることがより好ましく、０．８～１．２であることがさらに好ましい。前記当量比が３以下であると誘電特性をより向上できる。また、前記当量比が０．２以上であると、耐熱性が好ましく向上する。 The mixing ratio of the epoxy resin and the active ester compound is preferably such that, for example, the equivalent ratio of the epoxy group of the epoxy resin to the ester group of the active ester compound (epoxy group / ester group) is 0.2 to 3. 0.5 to 1.5 is more preferable, and 0.8 to 1.2 is more preferable. When the equivalent ratio is 3 or less, the dielectric properties can be further improved. Further, when the equivalent ratio is 0.2 or more, heat resistance is preferably improved.
　また、エポキシ樹脂のエポキシ基と活性エステル化合物のエステル基の当量比（エポキシ基／エステル基）の値にもよるが、エポキシ樹脂組成物中のエポキシ樹脂１００質量部に対して、活性エステル化合物は、例えば、好ましくは５０～２００質量部、より好ましくは７５～１７５質量部、さらに好ましくは８０～１５０質量部配合することができる。 Moreover, depending on the value of the equivalent ratio of the epoxy group of the epoxy resin and the ester group of the active ester compound (epoxy group / ester group), the active ester compound is based on 100 parts by mass of the epoxy resin in the epoxy resin composition. For example, 50 to 200 parts by mass, preferably 75 to 175 parts by mass, and more preferably 80 to 150 parts by mass can be blended.
　本発明のエポキシ樹脂組成物において、式（１）で表されるエポキシ樹脂は単独で又は２種以上を組み合わせて用いることができる。また、上述の通り活性エステル化合物も単独で又は２種以上を組み合わせて用いることができる。 In the epoxy resin composition of the present invention, the epoxy resin represented by the formula (1) can be used alone or in combination of two or more. Moreover, as above-mentioned, an active ester compound can also be used individually or in combination of 2 or more types.
　本発明のエポキシ樹脂組成物は、さらに硬化触媒を含んでいてもよい。特に、式（１）で表されるエポキシ樹脂の架橋反応を促進するものや、前記式（１）表されるエポキシ樹脂と活性エステル化合物との架橋反応を促進するものであれば特に限定されない。 The epoxy resin composition of the present invention may further contain a curing catalyst. In particular, it is not particularly limited as long as it promotes the crosslinking reaction of the epoxy resin represented by the formula (1), or promotes the crosslinking reaction between the epoxy resin represented by the formula (1) and the active ester compound.
　前記硬化触媒として、例えば、イミダゾール化合物、ジシアンジアミド、第三級アミン、リン系化合物、ルイス酸化合物、カチオン重合開始剤等が挙げられる。 Examples of the curing catalyst include imidazole compounds, dicyandiamides, tertiary amines, phosphorus compounds, Lewis acid compounds, and cationic polymerization initiators.
　本発明のエポキシ樹脂組成物は、本発明の効果を損なわない範囲で、前記式（１）表されるエポキシ樹脂以外のエポキシ樹脂を含有していてもよい。該エポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、脂環式エポキシ樹脂、臭素化エポキシ樹脂、トリグリシジルイソシアヌレート、水添ビスフェノールＡ型エポキシ樹脂、脂肪族系エポキシ樹脂、グリシジルエーテル型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビフェニル型エポキシ樹脂、ジシクロ型エポキシ樹脂、ナフタレン型エポキシ樹脂等を用いることができる。これらのエポキシ樹脂は単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 The epoxy resin composition of the present invention may contain an epoxy resin other than the epoxy resin represented by the formula (1) as long as the effects of the present invention are not impaired. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated epoxy resin, triglycidyl isocyanurate, hydrogenated Bisphenol A type epoxy resins, aliphatic epoxy resins, glycidyl ether type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins, dicyclo type epoxy resins, naphthalene type epoxy resins and the like can be used. These epoxy resins may be used alone or in combination of two or more.
　式（１）で表されるエポキシ樹脂以外のエポキシ樹脂を配合する場合、式（１）で表されるエポキシ樹脂と、式（１）で表されるエポキシ樹脂以外のエポキシ樹脂との配合比率は、質量比で、例えば１００：０～２０：８０であり、好ましくは１００：０～３０：７０であり、より好ましくは１００：０～４０：６０である。 When blending an epoxy resin other than the epoxy resin represented by formula (1), the blending ratio of the epoxy resin represented by formula (1) and the epoxy resin other than the epoxy resin represented by formula (1) is The mass ratio is, for example, 100: 0 to 20:80, preferably 100: 0 to 30:70, and more preferably 100: 0 to 40:60.
　本発明のエポキシ樹脂組成物は、本発明の目的や効果を損なわない範囲で、必要に応じてフィラー、硬化剤、熱可塑性樹脂、添加剤等を含有してもよい。 The epoxy resin composition of the present invention may contain a filler, a curing agent, a thermoplastic resin, an additive, and the like as necessary within a range that does not impair the object and effect of the present invention.
　前記フィラーとしては、該フィラーとしては、組成物及び硬化物において必要とされる流動性、耐熱性、低熱膨張性、機械特性、硬度、耐擦傷性及び接着性などを考慮し、単独で、又は複数種を混合して用いることができる。例えば、シリカ（より具体的には結晶性シリカ、溶融シリカ、球状溶融シリカ等）、酸化チタン、酸化ジルコニウム、酸化亜鉛、酸化スズ、窒化珪素、炭化珪素、窒化ホウ素、炭酸カルシウム、珪酸カルシウム、チタン酸カリウム、窒化アルミニウム、酸化インジウム、アルミナ、酸化アンチモン、酸化セリウム、酸化マグネシウム、酸化鉄、スズドープ酸化インジウム（ＩＴＯ）などの無機化合物が挙げられる。また、金、銀、銅、アルミニウム、ニッケル、鉄、亜鉛、ステンレスなどの金属が挙げられる。また、モンモリロナイト、タルク、マイカ、ベーマイト、カオリン、スメクタイト、ゾノライト、バーキュライト、セリサイトなどの鉱物が挙げられる。その他のフィラーとしては、カーボンブラック、アセチレンブラック、ケッチェンブラック、カーボンナノチューブなどの炭素化合物；水酸化アルミニウム、水酸化マグネシウムなどの金属水酸化物；ガラスビーズ、ガラスフレーク、ガラスバルーンなどの各種ガラスなどを挙げることができる。また、フィラーは粉体をそのまま使用してもよく、樹脂中に分散させたものを用いてもよい。 As the filler, considering the fluidity, heat resistance, low thermal expansion property, mechanical properties, hardness, scratch resistance, adhesiveness, etc. required for the composition and cured product, the filler alone or A plurality of types can be mixed and used. For example, silica (more specifically, crystalline silica, fused silica, spherical fused silica, etc.), titanium oxide, zirconium oxide, zinc oxide, tin oxide, silicon nitride, silicon carbide, boron nitride, calcium carbonate, calcium silicate, titanium Examples include inorganic compounds such as potassium acid, aluminum nitride, indium oxide, alumina, antimony oxide, cerium oxide, magnesium oxide, iron oxide, and tin-doped indium oxide (ITO). Moreover, metals, such as gold | metal | money, silver, copper, aluminum, nickel, iron, zinc, stainless steel, are mentioned. In addition, minerals such as montmorillonite, talc, mica, boehmite, kaolin, smectite, zonolite, verculite, and sericite can be mentioned. Other fillers include carbon compounds such as carbon black, acetylene black, ketjen black and carbon nanotubes; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; various glasses such as glass beads, glass flakes and glass balloons Can be mentioned. Further, the filler may be used as it is, or a filler dispersed in a resin may be used.
　前記硬化剤としては、例えば、アミン系硬化剤、アミド系硬化剤、酸無水物系硬化剤、フェノール系硬化剤、メルカプタン系硬化剤、イソシアネート系硬化剤、シアネートエステル系硬化剤などが挙げられる。硬化剤は、単独で用いてもよく、また、求める特性に応じて使い分けることが可能であり、２種以上を併用してもよい。 Examples of the curing agent include amine curing agents, amide curing agents, acid anhydride curing agents, phenol curing agents, mercaptan curing agents, isocyanate curing agents, and cyanate ester curing agents. A hardening | curing agent may be used independently, and can be used properly according to the characteristic to request | require, and may use 2 or more types together.
　アミン系硬化剤として、例えば、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミンなどの鎖状脂肪族アミン；イソフォロンジアミン、ベンゼンジアミン、ビス（４－アミノシクロヘキシル）メタン、ビス（アミノメチル）シクロヘキサン、ジアミノジシクロヘキシルメタンなどの脂環式アミン；メタフェニレンジアミン、ジアミノジフェニルメタン、ジエチルトルエンジアミン、ジアミノジエチルジフェニルメタンなどの芳香族アミン；ベンジルジメチルアミン、トリエチレンジアミン、ピペリジン、２－（ジメチルアミノメチル）フェノール、２，４，６－トリス（ジメチルアミノメチル）フェノール、ＤＢＵ（１，８－ジアザビシクロ（５，４，０）－ウンデセン－７）、ＤＢＮ（１，５－ジアザビシクロ（４，３，０）－ノネン－５）、などの第二級及び三級アミン等が挙げられる。 Examples of amine curing agents include chain aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; isophoronediamine, benzenediamine, bis (4-aminocyclohexyl) methane, and bis (aminomethyl) cyclohexane. Alicyclic amines such as diaminodicyclohexylmethane; aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, diethyltoluenediamine, diaminodiethyldiphenylmethane; benzyldimethylamine, triethylenediamine, piperidine, 2- (dimethylaminomethyl) phenol, 2 , 4,6-Tris (dimethylaminomethyl) phenol, DBU (1,8-diazabicyclo (5,4,0) -undecene-7), DBN (1, - diazabicyclo (4,3,0) - nonene-5), and a secondary and tertiary amines, such as.
　アミド系硬化剤として、例えば、ジシアンジアミド及びその誘導体、ポリアミド樹脂（ポリアミノアミド等）等が挙げられる。 Examples of amide-based curing agents include dicyandiamide and its derivatives, polyamide resins (polyaminoamide, etc.), and the like.
　酸無水物系硬化剤として、例えば、無水マレイン酸、ドデセニル無水コハク酸などの脂肪族酸無水物；無水フタル酸、無水トリメリット酸、無水ピロメリット酸などの芳香族酸無水物；無水メチルナジック酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、４－メチルヘキサヒドロ無水フタル酸などの脂環式酸無水物等が挙げられる。 Examples of acid anhydride curing agents include aliphatic acid anhydrides such as maleic anhydride and dodecenyl succinic anhydride; aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride; methyl nadic anhydride And alicyclic acid anhydrides such as acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 4-methylhexahydrophthalic anhydride.
　フェノール系硬化剤として、例えば、フェノールノボラック樹脂、クレゾールノボラック樹脂、ビフェニル型ノボラック樹脂、トリフェニルメタン型フェノール樹脂、ナフトールノボラック樹脂、フェノールビフェニレン樹脂、フェノールアラルキル樹脂、ビフェニルアラルキル型フェノール樹脂、変性ポリフェニレンエーテル樹脂、ベンゾオキサジン環を有する化合物等が挙げられる。 Examples of phenolic curing agents include phenol novolak resins, cresol novolak resins, biphenyl type novolak resins, triphenylmethane type phenol resins, naphthol novolak resins, phenol biphenylene resins, phenol aralkyl resins, biphenyl aralkyl type phenol resins, and modified polyphenylene ether resins. And compounds having a benzoxazine ring.
　メルカプタン系硬化剤として、例えば、トリメチロールプロパントリス（３－メルカプトプロピオネート）、トリス－［（３－メルカプトプロピオニルオキシ）－エチル］－イソシアヌレート、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、テトラエチレングリコールビス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、１，４－ビス（３－メルカプトブチリルオキシ）ブタン、トリメチロールプロパントリス（３－メルカプトブチレート）、トリメチロールエタントリス（３－メルカプトブチレート）、ポリサルファイドポリマー等が挙げられる。 Examples of mercaptan curing agents include trimethylolpropane tris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), Tetraethylene glycol bis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercaptobutyrate) , Trimethylol ethane tris (3-mercaptobutyrate), polysulfide polymer and the like.
　イソシアネート系硬化剤として、例えば、ヘキサメチレンジイソシアネート、１，４－テトラメチレンジイソシアネート、２－メチルペンタン－１，５－ジイソシアネート、リジンジイソシアネート、イソホロンジイソシアネート、ノルボルナンジイソシアネート等が挙げられる。 Examples of the isocyanate curing agent include hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, lysine diisocyanate, isophorone diisocyanate, and norbornane diisocyanate.
　前記熱可塑性樹脂としては、例えば、ポリオレフィン樹脂、アクリル樹脂、フェノキシ樹脂、ポリアミド樹脂、ポリエステル樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、ポリアリレート樹脂、ポリフェニレンエーテル樹脂、ポリアセタール樹脂、およびこれらが酸変性されたもの等が挙げられる。本発明にかかるエポキシ樹脂組成物との相溶性および耐熱性の観点から、ポリオレフィン樹脂、アクリル樹脂、フェノキシ樹脂、ポリアリレート樹脂、ポリフェニレンエーテル樹脂、およびこれらが酸変性されたものが好ましく、これらの中でもポリオレフィン樹脂、酸変性ポリオレフィン樹脂がさらに好ましい。 Examples of the thermoplastic resin include polyolefin resin, acrylic resin, phenoxy resin, polyamide resin, polyester resin, polycarbonate resin, polyurethane resin, polyarylate resin, polyphenylene ether resin, polyacetal resin, and those obtained by acid modification. Is mentioned. From the viewpoint of compatibility with the epoxy resin composition according to the present invention and heat resistance, polyolefin resins, acrylic resins, phenoxy resins, polyarylate resins, polyphenylene ether resins, and those obtained by acid modification are preferred, among these More preferred are polyolefin resins and acid-modified polyolefin resins.
　前記添加剤としては、例えば、酸化防止剤、無機蛍光体、滑剤、紫外線吸収剤、熱光安定剤、帯電防止剤、重合禁止剤、消泡剤、溶剤、老化防止剤、ラジカル禁止剤、接着性改良剤、難燃剤、界面活性剤、保存安定性改良剤、オゾン老化防止剤、増粘剤、可塑剤、放射線遮断剤、核剤、カップリング剤、導電性付与剤、リン系過酸化物分解剤、顔料、金属不活性化剤、物性調整剤等が挙げられる。 Examples of the additive include an antioxidant, an inorganic phosphor, a lubricant, an ultraviolet absorber, a heat and light stabilizer, an antistatic agent, a polymerization inhibitor, an antifoaming agent, a solvent, an antiaging agent, a radical inhibitor, and an adhesive. Property improver, flame retardant, surfactant, storage stability improver, ozone anti-aging agent, thickener, plasticizer, radiation blocker, nucleating agent, coupling agent, conductivity imparting agent, phosphorus peroxide Examples include decomposing agents, pigments, metal deactivators, and physical property modifiers.
　本発明のエポキシ樹脂組成物は、式（１）で表されるエポキシ樹脂及び活性エステル化合物、さらに必要に応じて他の成分を混合することにより製造することができる。混合方法は、均一に混合できる方法であれば特に限定はない。本発明のエポキシ樹脂組成物には、必要に応じ、本発明の効果に悪影響を与えない範囲で溶剤（例えば、トルエン、キシレン、メチルエチルケトン、アセトン、シクロヘキサノン、メチルシクロヘキサン、シクロヘキサン等）を添加してもよい。 The epoxy resin composition of the present invention can be produced by mixing the epoxy resin represented by the formula (1) and the active ester compound and, if necessary, other components. The mixing method is not particularly limited as long as it can be uniformly mixed. If necessary, a solvent (for example, toluene, xylene, methyl ethyl ketone, acetone, cyclohexanone, methylcyclohexane, cyclohexane, etc.) may be added to the epoxy resin composition of the present invention as long as the effects of the present invention are not adversely affected. Good.
　本発明のエポキシ樹脂組成物を硬化することにより硬化物（すなわち、当該エポキシ樹脂組成物の硬化物）を得ることができる。硬化の方法は、特に限定されず、例えば、該組成物を加熱硬化することで実施できる。硬化温度は、通常室温～３００℃であり、硬化時間は、組成液によって異なり、通常３０分～１週間まで幅広く設定することができる。 A cured product (that is, a cured product of the epoxy resin composition) can be obtained by curing the epoxy resin composition of the present invention. The curing method is not particularly limited, and can be carried out, for example, by heat curing the composition. The curing temperature is usually room temperature to 300 ° C., and the curing time varies depending on the composition liquid, and can be set widely from 30 minutes to 1 week.
　なお、本明細書において「含む」とは、「本質的にからなる」と、「からなる」をも包含する（The term "comprising" includes "consisting essentially of” and "consisting of."）。 In this specification, “including” also includes “consisting essentially of” and “consisting of” (The term “comprising” “includes” “consisting” essentially “of” “and” “consisting” of.).
　以下、本発明をより具体的に説明するが、本発明は下記の例に限定されるものではない。 Hereinafter, the present invention will be described more specifically, but the present invention is not limited to the following examples.
製造例１（エポキシ樹脂Ａの製造）
　攪拌機、温度計及び冷却器を備え付けた２００ｍＬ容の四つ口フラスコに、窒素雰囲気下で、アリルグリシジルエーテル５．９ｇ、ヘキサクロロ白金酸六水和物の２ｗｔ％エタノール溶液０．０５ｇ、トルエン１００ｇを仕込み、液温を７０℃まで昇温させた。その後、１，４－ビス（ジメチルシリル）ベンゼン５．０ｇを１５分間で滴下し、引続き、９０℃で４時間攪拌した。トルエンを濃縮により除去後、無色透明液体の１，４－ビス［（２，３－エポキシプロピルオキシプロピル）ジメチルシリル］ベンゼン（エポキシ樹脂Ａ）１０．３ｇ（エポキシ当量２１１ｇ／ｅｑ）を取得した。 Production Example 1 (Production of Epoxy Resin A)
In a 200 mL four-necked flask equipped with a stirrer, a thermometer, and a condenser, under a nitrogen atmosphere, 5.9 g of allyl glycidyl ether, 0.05 g of a 2 wt% ethanol solution of hexachloroplatinic acid hexahydrate, and 100 g of toluene were added. First, the liquid temperature was raised to 70 ° C. Thereafter, 5.0 g of 1,4-bis (dimethylsilyl) benzene was added dropwise over 15 minutes, followed by stirring at 90 ° C. for 4 hours. After removing toluene by concentration, 10.3 g (epoxy equivalent 211 g / eq) of 1,4-bis [(2,3-epoxypropyloxypropyl) dimethylsilyl] benzene (epoxy resin A) as a colorless transparent liquid was obtained.
製造例２（エポキシ樹脂Ｂの製造）
　攪拌機、温度計及び冷却器を備え付けた２００ｍＬ容の四つ口フラスコに、窒素雰囲気下で、１，２－エポキシ－５－ヘキセン５．０ｇ、ヘキサクロロ白金酸六水和物の２ｗｔ％エタノール溶液０．０５ｇ、トルエン１００ｇを仕込み、液温を７０℃まで昇温させた。その後、１，４－ビス（ジメチルシリル）ベンゼン５．０ｇを１５分間で滴下し、引続き、９０℃で５時間攪拌した。トルエンを濃縮により除去後、無色透明液体の１，４－ビス［（２，３－エポキシブチル）ジメチルシリル］ベンゼン（エポキシ樹脂Ｂ）９．５ｇ（エポキシ当量１９５ｇ／ｅｑ）を取得した。 Production Example 2 (Production of Epoxy Resin B)
In a 200 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, under a nitrogen atmosphere, 5.0 g of 1,2-epoxy-5-hexene, 2 wt% ethanol solution of hexachloroplatinic acid hexahydrate 0 0.05 g and 100 g of toluene were charged, and the liquid temperature was raised to 70 ° C. Thereafter, 5.0 g of 1,4-bis (dimethylsilyl) benzene was added dropwise over 15 minutes, followed by stirring at 90 ° C. for 5 hours. After removing toluene by concentration, 9.5 g (epoxy equivalent 195 g / eq) of 1,4-bis [(2,3-epoxybutyl) dimethylsilyl] benzene (epoxy resin B) as a colorless transparent liquid was obtained.
製造例３（エポキシ樹脂Ｃの製造）
　攪拌機、温度計及び冷却器を備え付けた２００ｍＬ容の四つ口フラスコに、窒素雰囲気下で、１，２－エポキシ－４－ビニルシクロヘキサン６．４ｇ、ヘキサクロロ白金酸六水和物の２ｗｔ％エタノール溶液０．０５ｇ、トルエン１００ｇを仕込み、液温を７０℃まで昇温させた。その後、１，４－ビス（ジメチルシリル）ベンゼン５．０ｇを１５分間で滴下し、引続き、９０℃で４時間攪拌した。トルエンを濃縮により除去後、無色透明液体の１，４－ビス｛［２－（３，４－エポキシシクロヘキシル）エチル]ジメチルシリル｝ベンゼン（エポキシ樹脂Ｃ）１０．８ｇ（エポキシ当量２２１ｇ／ｅｑ）を取得した。 Production Example 3 (Production of epoxy resin C)
In a 200 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 6.4 g of 1,2-epoxy-4-vinylcyclohexane and 2 wt% ethanol solution of hexachloroplatinic acid hexahydrate in a nitrogen atmosphere 0.05 g and 100 g of toluene were charged, and the liquid temperature was raised to 70 ° C. Thereafter, 5.0 g of 1,4-bis (dimethylsilyl) benzene was added dropwise over 15 minutes, followed by stirring at 90 ° C. for 4 hours. After removing the toluene by concentration, 10.8 g (epoxy equivalent 221 g / eq) of 1,4-bis {[2- (3,4-epoxycyclohexyl) ethyl] dimethylsilyl} benzene (epoxy resin C) as a colorless transparent liquid was added. I got it.
製造例４（エポキシ樹脂Ｄの製造）
攪拌機、温度計及び冷却器を備え付けた２００ｍＬ容の四つ口フラスコに、窒素雰囲気下で、１，２－エポキシ－４－ビニルシクロヘキサン４．３ｇ、ヘキサクロロ白金酸六水和物の２ｗｔ％エタノール溶液０．０５ｇ、トルエン２５０ｇを仕込み、液温を７０℃まで昇温させたた。その後、ビス[（ｐ－ジメチルシリル）フェニル]エーテル５．０ｇを１５分間で滴下し、引続き、９０℃で６時間攪拌した。トルエンを濃縮により除去後、無色透明液体の４，４’－ビス｛［２－（３，４－エポキシシクロヘキシル）エチル]ジメチルシリル｝ジフェニルエーテル（エポキシ樹脂Ｄ）８．９ｇ（エポキシ当量２６７ｇ／ｅｑ）を取得した。 Production Example 4 (Production of epoxy resin D)
In a 200 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 4.3 g of 1,2-epoxy-4-vinylcyclohexane and a 2 wt% ethanol solution of hexachloroplatinic acid hexahydrate under a nitrogen atmosphere 0.05 g and 250 g of toluene were charged, and the liquid temperature was raised to 70 ° C. Thereafter, 5.0 g of bis [(p-dimethylsilyl) phenyl] ether was added dropwise over 15 minutes, followed by stirring at 90 ° C. for 6 hours. After removing toluene by concentration, 8.9 g (epoxy resin equivalent 267 g / eq) of 4,4′-bis {[2- (3,4-epoxycyclohexyl) ethyl] dimethylsilyl} diphenyl ether (epoxy resin D) as a colorless transparent liquid Acquired.
製造例５（エポキシ樹脂Ｅの製造）
攪拌機、温度計及び冷却器を備え付けた２００ｍＬ容の四つ口フラスコに、窒素雰囲気下で、１，２－エポキシ－４－ビニルシクロヘキサン７．４ｇ、ヘキサクロロ白金酸六水和物の２ｗｔ％エタノール溶液０．０５ｇ、トルエン２５０ｇを仕込み、液温を７０℃まで昇温させた。その後、１，３，５－トリス（ジメチルシリル）ベンゼン５．０ｇを１５分間で滴下し、引続き、９０℃で６時間攪拌した。トルエンを濃縮により除去後、無色透明液体の１，３，５－トリス｛［２－（３，４－エポキシシクロヘキシル）エチル]ジメチルシリル｝ベンゼン（エポキシ樹脂Ｅ）１１．８ｇ（エポキシ当量２０８ｇ／ｅｑ）を取得した。 Production Example 5 (Production of epoxy resin E)
In a 200 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, 7.4 g of 1,2-epoxy-4-vinylcyclohexane and a 2 wt% ethanol solution of hexachloroplatinic acid hexahydrate in a nitrogen atmosphere 0.05 g and 250 g of toluene were charged, and the liquid temperature was raised to 70 ° C. Thereafter, 5.0 g of 1,3,5-tris (dimethylsilyl) benzene was added dropwise over 15 minutes, followed by stirring at 90 ° C. for 6 hours. After removing the toluene by concentration, 11.8 g of an colorless transparent liquid 1,3,5-tris {[2- (3,4-epoxycyclohexyl) ethyl] dimethylsilyl} benzene (epoxy resin E) (epoxy equivalent 208 g / eq) ).
実施例、比較例
　表２及び表３に記載した配合量の各成分をナス型フラスコに秤量し、マグネチックスターラーにて、室温（２５℃）で５分間攪拌した。その後、６０℃に加熱しながら減圧下でトルエン（活性エステル化合物の溶剤）を留去し、エポキシ樹脂組成物を調製した。 Examples and Comparative Examples Each component having the blending amounts shown in Tables 2 and 3 was weighed in an eggplant type flask and stirred with a magnetic stirrer at room temperature (25 ° C.) for 5 minutes. Thereafter, toluene (the solvent for the active ester compound) was distilled off under reduced pressure while heating at 60 ° C. to prepare an epoxy resin composition.
　表２及び表３中の各成分は以下の通りである。なお、表２及び表３の各成分の数値は、質量部を示す。 Each component in Table 2 and Table 3 is as follows. In addition, the numerical value of each component of Table 2 and Table 3 shows a mass part.
・エポキシ樹脂Ｆ：三菱化学社製Ｂｉｓ－Ａ型エポキシ樹脂（グレード８２８）（エポキシ当量１８９ｇ／ｅｑ）
・エポキシ樹脂Ｇ：ダイセル社製脂環式エポキシ樹脂（セロキサイド２０２１Ｐ；一般名は3',4'-エポキシシクロヘキシルメチル 3,4-エポキシシクロヘキサンカルボキシレート
）（エポキシ当量１３７ｇ／ｅｑ）
・活性エステル化合物：ＤＩＣ社製活性エステル樹脂ＥＰＩＣＬＯＮ　ＨＰＣ－８０００－６５Ｔ（トルエン溶液、固形分濃度６５％、エステル当量 約２２３ｇ／ｅｑ）
・硬化触媒：東京化成社製４－ジメチルアミノピリジン（ＤＭＡＰ） Epoxy resin F: Bis-A type epoxy resin (grade 828) manufactured by Mitsubishi Chemical Corporation (epoxy equivalent 189 g / eq)
Epoxy resin G: Alicyclic epoxy resin manufactured by Daicel (Celoxide 2021P; generic name is 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate) (epoxy equivalent 137 g / eq)
Active ester compound: Active ester resin EPICLON HPC-8000-65T manufactured by DIC (toluene solution, solid content concentration 65%, ester equivalent of about 223 g / eq)
Curing catalyst: 4-dimethylaminopyridine (DMAP) manufactured by Tokyo Chemical Industry Co., Ltd.
　得られた各実施例及び比較例のエポキシ樹脂組成物について、以下の項目について評価した。なお、各評価の結果を表２及び表３に併せて示す。 The following items were evaluated for the epoxy resin compositions of the obtained Examples and Comparative Examples. In addition, the result of each evaluation is combined with Table 2 and Table 3, and is shown.
（１）耐熱性（ガラス転移温度）
各実施例及び比較例で得られたエポキシ樹脂組成物をモールドに注型し、１００℃で１時間、１２０℃で２時間、１５０℃で２時間加熱して硬化させた。得られた試験片について、熱機械分析装置（ＳＳＣ５２００、エスエスアイ・ナノテクノロジー社製）を用いて、圧縮モード、荷重５０ｍＮ、５℃／ｍｉｎでガラス転移温度を測定した。 (1) Heat resistance (glass transition temperature)
The epoxy resin compositions obtained in each Example and Comparative Example were cast into a mold and cured by heating at 100 ° C. for 1 hour, 120 ° C. for 2 hours, and 150 ° C. for 2 hours. About the obtained test piece, the glass transition temperature was measured by the compression mode and the load of 50 mN, 5 degree-C / min using the thermomechanical analyzer (SSC5200, SSI nanotechnology company make).
（２）銅箔に対する９０度ピール強度
各実施例及び比較例で得られたエポキシ樹脂組成物をアルミ板に塗布し、その上から厚さ３５μｍの電解銅箔（古河電気工業社製）を重ね合わせた。１００℃で１時間、１２０℃で２時間、１５０℃で２時間加熱して硬化させた。硬化後、硬化物を幅１ｃｍになるようにカッターで切れ目を入れ、９０度ピール強度試験片とした。得られた試験片について、ＡＧＳ－Ｘ（島津製作所社製）を用いて、試験速度５０ｍｍ／ｍｉｎの条件で９０度ピール強度試験を実施した。 (2) 90 degree peel strength with respect to copper foil The epoxy resin composition obtained in each example and comparative example was applied to an aluminum plate, and a 35 μm thick electrolytic copper foil (manufactured by Furukawa Electric Co., Ltd.) was stacked thereon. Combined. It was cured by heating at 100 ° C. for 1 hour, 120 ° C. for 2 hours, and 150 ° C. for 2 hours. After curing, the cured product was cut with a cutter so as to have a width of 1 cm to obtain a 90-degree peel strength test piece. The obtained test piece was subjected to a 90 degree peel strength test using AGS-X (manufactured by Shimadzu Corporation) at a test speed of 50 mm / min.
（３）電気特性（誘電正接）
　実施例及び比較例で得られた各エポキシ樹脂組成物を樹脂製モールド（厚さ２ｍｍ）に流し込み、１００℃で１時間、１２０℃で２時間、１５０℃で２時間加熱して硬化させた。次いで、硬化物を幅２０ｍｍ×長さ３０ｍｍ×厚さ２ｍｍのサイズに切り出し、試験片とした。得られた試験片は、誘電率測定装置（インピーダンスアナライザー、アジレント社製）を用いて、２５℃にて、誘電正接（１ＧＨｚ）を測定した。また、誘電率測定装置の校正は、ＰＴＦＥを用いて行った。 (3) Electrical characteristics (dielectric loss tangent)
Each epoxy resin composition obtained in Examples and Comparative Examples was poured into a resin mold (thickness 2 mm), and cured by heating at 100 ° C. for 1 hour, 120 ° C. for 2 hours, and 150 ° C. for 2 hours. Next, the cured product was cut into a size of width 20 mm × length 30 mm × thickness 2 mm to obtain a test piece. The obtained test piece was measured for dielectric loss tangent (1 GHz) at 25 ° C. using a dielectric constant measuring apparatus (impedance analyzer, manufactured by Agilent). The dielectric constant measuring apparatus was calibrated using PTFE.
Figure JPOXMLDOC01-appb-T000069
Figure JPOXMLDOC01-appb-T000069
Figure JPOXMLDOC01-appb-T000070
Figure JPOXMLDOC01-appb-T000070

Claims (9)

  1. 式（１）：
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｘ環は
    飽和炭化水素環又は不飽和炭化水素環、あるいは
    飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合又は２個連結した構造を有する環
    であり、
    ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、同一又は異なって、水素原子、低級アルキル基、低級アルコキシ基、低級アルケニル基、ハロゲン原子、又は式（３）：
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ１は同一又は異なって、炭素数１～１８のアルキル基、炭素数２～９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基を示し、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
    　Ｒ２は、炭素数１～１８のアルキレン基を示し、この基は、ケイ素原子に直接結合した炭素原子を除く一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
    　Ｒ３は同一又は異なって、炭素数１～１８のアルキル基、炭素数２～９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基を示し、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
    ｍは０～６の整数を示し、
    ｎは０～３の整数を示す。）で表される基を示し、
    但し、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄのうち、少なくとも１つは式（３）で表される基であり、
    Ｘ環を構成する炭化水素環を構成する炭素原子であって且つＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄが結合していない炭素原子に結合した水素原子が、低級アルキル基、低級アルコキシ基、低級アルケニル基、又はハロゲン原子で置換されていてもよい。）
    で表されるエポキシ樹脂と活性エステル化合物とを含有するエポキシ樹脂組成物。     Formula (1):
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, the ring X is a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed or connected,
    R Xa , R Xb , R Xc , and R Xd are the same or different and are a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyl group, a halogen atom, or formula (3):
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, R 1 is the same or different and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. The carbon atom may be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom;
    R 2 represents an alkylene group having 1 to 18 carbon atoms, and this group is at least one selected from the group consisting of oxygen atoms and nitrogen atoms, with some carbon atoms excluding carbon atoms directly bonded to silicon atoms. May be substituted with
    R 3 s are the same or different and each represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and these groups have a part of carbon atoms, May be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom,
    m represents an integer of 0 to 6,
    n represents an integer of 0 to 3. )
    However, at least one of R Xa , R Xb , R Xc , and R Xd is a group represented by the formula (3),
    A hydrogen atom bonded to a carbon atom constituting a hydrocarbon ring constituting the X ring and to which R Xa , R Xb , R Xc , and R Xd are not bonded is a lower alkyl group or a lower alkoxy group , A lower alkenyl group, or a halogen atom. )
    The epoxy resin composition containing the epoxy resin represented by these, and an active ester compound.
  2. 前記飽和炭化水素環及び／又は不飽和炭化水素環が２個連結した構造を有する環が、
    式（２）：
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｘ１環及びＸ２環は、同一又は異なって、飽和炭化水素環又は不飽和炭化水素環を示し、Ｙは、結合手、炭素数１～４のアルキル基で置換されていてもよい炭素数１～６のアルキレン基、酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、－ＳＯ－、又は－ＳＯ２－を示す。）で表される環である、請求項１に記載のエポキシ樹脂組成物。     A ring having a structure in which two saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are connected,
    Formula (2):
    Figure JPOXMLDOC01-appb-C000003
     (Wherein, ring X 1 and ring X 2 are the same or different and each represents a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, and Y is a bond, substituted with an alkyl group having 1 to 4 carbon atoms. Or a ring represented by an alkylene group having 1 to 6 carbon atoms, an oxygen atom (—O—), a sulfur atom (—S—), —SO—, or —SO 2 —). 2. The epoxy resin composition according to 1.
  3. 前記飽和炭化水素環が炭素数４～８の飽和炭化水素環であり、
    前記不飽和炭化水素環が炭素数４～８の不飽和炭化水素環である、
    請求項１又は２に記載のエポキシ樹脂組成物。     The saturated hydrocarbon ring is a saturated hydrocarbon ring having 4 to 8 carbon atoms;
    The unsaturated hydrocarbon ring is an unsaturated hydrocarbon ring having 4 to 8 carbon atoms;
    The epoxy resin composition according to claim 1 or 2.
  4. 式（１－ｉｉａ）：
    Figure JPOXMLDOC01-appb-C000004
     （式中、Ｘｉｉは、飽和炭化水素環若しくは不飽和炭化水素環、又は飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合した構造を有する環、から２個の水素原子を除いて得られる２価の基、あるいは式（２ｇ－ｉｉａ）：
    Figure JPOXMLDOC01-appb-C000005
     （式中、Ｙは、結合手、炭素数１～４のアルキル基で置換されていてもよい炭素数１～６のアルキレン基、酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、－ＳＯ－、又は－ＳＯ２－を示す。）で表される２価の基を示し、
    Ｒ１は同一又は異なって、炭素数１～１８のアルキル基、炭素数２～９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基を示し、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
    　Ｒ２は同一又は異なって、炭素数１～１８のアルキレン基を示し、この基は、ケイ素原子に直接結合した炭素原子を除く一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
    　Ｒ３は同一又は異なって、炭素数１～１８のアルキル基、炭素数２～９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基を示し、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
    ｍは０～６の整数を示し、
    ｎは０～３の整数を示す。）
    で表されるエポキシ樹脂、並びに
    式（１－ｉｉｉａ）：
    Figure JPOXMLDOC01-appb-C000006
     （式中、Ｘｉｉｉは、飽和炭化水素環若しくは不飽和炭化水素環、又は飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合した構造を有する環、から３個の水素原子を除いて得られる３価の基、又は式（２ｇ－ｉｉｉａ）：
    Figure JPOXMLDOC01-appb-C000007
     （式中、Ｙは、前記に同じ。）で表される３価の基を示し、
    Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは前記に同じ。）
    で表されるエポキシ樹脂
    からなる群より選択される少なくとも１種のエポキシ樹脂と活性エステル化合物とを含有する請求項１に記載のエポキシ樹脂組成物。     Formula (1-ia):
    Figure JPOXMLDOC01-appb-C000004
     ( Wherein X ii represents a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed, to two hydrogen atoms A divalent group obtained by removing or a formula (2 g -ia):
    Figure JPOXMLDOC01-appb-C000005
     (Wherein Y represents a bond, an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, an oxygen atom (—O—), a sulfur atom (—S—), -SO- or -SO 2- )).
    R 1 s are the same or different and each represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and these groups have a part of carbon atoms, May be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom,
    R 2 is the same or different and represents an alkylene group having 1 to 18 carbon atoms, and this group is selected from the group consisting of oxygen atoms and nitrogen atoms, with some carbon atoms excluding carbon atoms directly bonded to silicon atoms. Optionally substituted with at least one atom
    R 3 s are the same or different and each represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and these groups have a part of carbon atoms, May be substituted with at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom,
    m represents an integer of 0 to 6,
    n represents an integer of 0 to 3. )
    And an epoxy resin represented by the formula (1-iiia):
    Figure JPOXMLDOC01-appb-C000006
     (In the formula, X iii is a saturated hydrocarbon ring or an unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and / or unsaturated hydrocarbon rings are condensed, to 3 hydrogen atoms A trivalent group obtained by removing or a formula (2 g -iiia):
    Figure JPOXMLDOC01-appb-C000007
     (Wherein Y represents the same as described above),
    R 1 , R 2 , R 3 , m, and n are the same as described above. )
    The epoxy resin composition of Claim 1 containing the at least 1 sort (s) of epoxy resin selected from the group which consists of epoxy resin represented by these, and an active ester compound.
  5. 活性エステル化合物が、エステル基を１分子中に２個以上有する化合物である、請求項１～４のいずれかに記載のエポキシ樹脂組成物。 The epoxy resin composition according to any one of claims 1 to 4, wherein the active ester compound is a compound having two or more ester groups in one molecule.
  6. 活性エステル化合物が、カルボン酸化合物及びチオカルボン酸化合物からなる群より選択される少なくとも１種と、ヒドロキシ化合物及びチオール化合物からなる群より選択される少なくとも１種との、縮合物である、請求項１～４のいずれかに記載のエポキシ樹脂組成物。 The active ester compound is a condensate of at least one selected from the group consisting of carboxylic acid compounds and thiocarboxylic acid compounds and at least one selected from the group consisting of hydroxy compounds and thiol compounds. 5. The epoxy resin composition according to any one of 4 to 4.
  7. 活性エステル化合物が、ジシクロペンタジエニルジフェノール構造を含むエステル化合物である、請求項１～４のいずれかに記載のエポキシ樹脂組成物。 The epoxy resin composition according to any one of claims 1 to 4, wherein the active ester compound is an ester compound containing a dicyclopentadienyl diphenol structure.
  8. 請求項１～７のいずれかに記載のエポキシ樹脂組成物の硬化物。 A cured product of the epoxy resin composition according to any one of claims 1 to 7.
  9. 請求項１～７のいずれかに記載のエポキシ樹脂組成物又は請求項８に記載の硬化物が用いられている半導体封止体、液状封止材、ポッティング材、シール材、層間絶縁膜、接着層、カバーレイフィルム、電磁波シールドフィルム、プリント基板材料又は複合材料。 A semiconductor encapsulant, a liquid encapsulant, a potting material, a sealing material, an interlayer insulating film, an adhesive, wherein the epoxy resin composition according to any one of claims 1 to 7 or the cured product according to claim 8 is used. Layer, coverlay film, electromagnetic shielding film, printed circuit board material or composite material.
PCT/JP2018/000200 2017-01-10 2018-01-09 Epoxy resin composition WO2018131569A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
KR1020197021281A KR102461516B1 (en) 2017-01-10 2018-01-09 epoxy resin composition
EP18738684.2A EP3569628B1 (en) 2017-01-10 2018-01-09 Epoxy resin composition
JP2018561366A JP6553310B2 (en) 2017-01-10 2018-01-09 Epoxy resin composition
US16/476,679 US20200385514A1 (en) 2017-01-10 2018-01-09 Epoxy resin composition
CN201880006382.5A CN110167989B (en) 2017-01-10 2018-01-09 Epoxy resin composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-002214 2017-01-10
JP2017002214 2017-01-10

Publications (1)

Publication Number Publication Date
WO2018131569A1 true WO2018131569A1 (en) 2018-07-19

Family

ID=62840577

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/000200 WO2018131569A1 (en) 2017-01-10 2018-01-09 Epoxy resin composition

Country Status (7)

Country Link
US (1) US20200385514A1 (en)
EP (1) EP3569628B1 (en)
JP (1) JP6553310B2 (en)
KR (1) KR102461516B1 (en)
CN (1) CN110167989B (en)
TW (1) TWI773723B (en)
WO (1) WO2018131569A1 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019026822A1 (en) * 2017-07-31 2019-02-07 住友精化株式会社 Epoxy resin composition
JP2020050793A (en) * 2018-09-27 2020-04-02 日立化成株式会社 Sealing resin composition, electronic component device and method for producing electronic component device
US11066510B2 (en) 2015-07-10 2021-07-20 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition, process for producing same, and uses of said composition
US11091627B2 (en) 2017-01-10 2021-08-17 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition
US11111382B2 (en) 2017-01-10 2021-09-07 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition
US11292872B2 (en) 2017-01-10 2022-04-05 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition
US11603466B2 (en) 2017-01-10 2023-03-14 Sumitomo Seika Chemicals Co.. Ltd. Epoxy resin composition
WO2023127709A1 (en) * 2021-12-27 2023-07-06 住友精化株式会社 Epoxy resin composition

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1123960A (en) 1966-03-02 1968-08-14 Dow Corning Organosilicon epoxides
JP2003519705A (en) * 2000-01-13 2003-06-24 スリーエム エスペ アーゲー Polymerizable preparations based on silicon-containing epoxides
JP2004527602A (en) * 2001-02-19 2004-09-09 スリーエム エスペ アーゲー Polymerizable formulations based on silicon compounds containing aliphatic and cycloaliphatic epoxide groups
JP2004277460A (en) 2003-03-12 2004-10-07 Tdk Corp Epoxy resin composition, and sheet, preperg-like material, sheet with metal foil, laminated sheet, electrical insulating material and resist material obtained therefrom
JP2008505945A (en) * 2004-07-14 2008-02-28 スリーエム イーエスピーイー アーゲー Dental composition comprising an epoxy functional carbosilane compound
JP2009235165A (en) 2008-03-26 2009-10-15 Dic Corp Epoxy resin composition and its cured product
JP2012001668A (en) * 2010-06-18 2012-01-05 Shin-Etsu Chemical Co Ltd Silphenylene-containing photocurable composition, method for forming pattern using the same, and optical semiconductor element obtained using the method
WO2013061688A1 (en) 2011-10-26 2013-05-02 味の素株式会社 Resin composition
WO2015041325A1 (en) * 2013-09-20 2015-03-26 信越化学工業株式会社 Silicone-modified epoxy resin and composition and cured article thereof
JP2016117904A (en) 2009-11-26 2016-06-30 味の素株式会社 Epoxy resin composition
WO2017010401A1 (en) * 2015-07-10 2017-01-19 住友精化株式会社 Epoxy resin composition, process for producing same, and uses of said composition
JP2017019983A (en) * 2015-07-10 2017-01-26 住友精化株式会社 Benzoxazine resin composition, method for producing the same, and use for the composition
WO2017086368A1 (en) * 2015-11-18 2017-05-26 住友精化株式会社 Epoxy resin composition, method for producing same, and use of composition

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1123960A (en) 1914-03-06 1915-01-05 Valentine Von Der Lin Furniture-tread.
JP6163803B2 (en) * 2013-03-14 2017-07-19 味の素株式会社 Resin composition
CN105315615B (en) * 2014-08-05 2017-11-21 广东生益科技股份有限公司 A kind of composition epoxy resin and the prepreg and copper-clad laminate using its making

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1123960A (en) 1966-03-02 1968-08-14 Dow Corning Organosilicon epoxides
JP2003519705A (en) * 2000-01-13 2003-06-24 スリーエム エスペ アーゲー Polymerizable preparations based on silicon-containing epoxides
JP2004527602A (en) * 2001-02-19 2004-09-09 スリーエム エスペ アーゲー Polymerizable formulations based on silicon compounds containing aliphatic and cycloaliphatic epoxide groups
JP2004277460A (en) 2003-03-12 2004-10-07 Tdk Corp Epoxy resin composition, and sheet, preperg-like material, sheet with metal foil, laminated sheet, electrical insulating material and resist material obtained therefrom
JP2008505945A (en) * 2004-07-14 2008-02-28 スリーエム イーエスピーイー アーゲー Dental composition comprising an epoxy functional carbosilane compound
JP2009235165A (en) 2008-03-26 2009-10-15 Dic Corp Epoxy resin composition and its cured product
JP2016117904A (en) 2009-11-26 2016-06-30 味の素株式会社 Epoxy resin composition
JP2012001668A (en) * 2010-06-18 2012-01-05 Shin-Etsu Chemical Co Ltd Silphenylene-containing photocurable composition, method for forming pattern using the same, and optical semiconductor element obtained using the method
WO2013061688A1 (en) 2011-10-26 2013-05-02 味の素株式会社 Resin composition
WO2015041325A1 (en) * 2013-09-20 2015-03-26 信越化学工業株式会社 Silicone-modified epoxy resin and composition and cured article thereof
WO2017010401A1 (en) * 2015-07-10 2017-01-19 住友精化株式会社 Epoxy resin composition, process for producing same, and uses of said composition
JP2017019983A (en) * 2015-07-10 2017-01-26 住友精化株式会社 Benzoxazine resin composition, method for producing the same, and use for the composition
WO2017086368A1 (en) * 2015-11-18 2017-05-26 住友精化株式会社 Epoxy resin composition, method for producing same, and use of composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3569628A4

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11066510B2 (en) 2015-07-10 2021-07-20 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition, process for producing same, and uses of said composition
US11091627B2 (en) 2017-01-10 2021-08-17 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition
US11111382B2 (en) 2017-01-10 2021-09-07 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition
US11292872B2 (en) 2017-01-10 2022-04-05 Sumitomo Seika Chemicals Co., Ltd. Epoxy resin composition
US11603466B2 (en) 2017-01-10 2023-03-14 Sumitomo Seika Chemicals Co.. Ltd. Epoxy resin composition
WO2019026822A1 (en) * 2017-07-31 2019-02-07 住友精化株式会社 Epoxy resin composition
JP2020050793A (en) * 2018-09-27 2020-04-02 日立化成株式会社 Sealing resin composition, electronic component device and method for producing electronic component device
WO2023127709A1 (en) * 2021-12-27 2023-07-06 住友精化株式会社 Epoxy resin composition

Also Published As

Publication number Publication date
CN110167989B (en) 2022-11-11
TW201831592A (en) 2018-09-01
KR102461516B1 (en) 2022-11-02
KR20190098756A (en) 2019-08-22
EP3569628B1 (en) 2021-08-11
TWI773723B (en) 2022-08-11
EP3569628A4 (en) 2020-07-22
CN110167989A (en) 2019-08-23
JP6553310B2 (en) 2019-07-31
US20200385514A1 (en) 2020-12-10
EP3569628A1 (en) 2019-11-20
JPWO2018131569A1 (en) 2019-07-11

Similar Documents

Publication Publication Date Title
JP6553310B2 (en) Epoxy resin composition
JP6553312B2 (en) Epoxy resin composition
CN110177819B (en) Epoxy resin composition
JP6556965B2 (en) Epoxy resin composition
US20200115554A1 (en) Epoxy resin composition, method for producing same, and use of composition
WO2018181719A1 (en) Epoxy resin, epoxy resin composition, and cured object obtained therefrom, use thereof, and production method therefor
WO2018131564A1 (en) Epoxy resin composition
CN114008104B (en) Epoxy resin composition
JP2024062263A (en) Epoxy resin composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18738684

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2018561366

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20197021281

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2018738684

Country of ref document: EP

Effective date: 20190812